CN103396828B - Polyether crude oil demulsifier using straight chain alkyl phenolic resin as initiator and preparation method and application thereof - Google Patents
Polyether crude oil demulsifier using straight chain alkyl phenolic resin as initiator and preparation method and application thereof Download PDFInfo
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- CN103396828B CN103396828B CN201310318303.3A CN201310318303A CN103396828B CN 103396828 B CN103396828 B CN 103396828B CN 201310318303 A CN201310318303 A CN 201310318303A CN 103396828 B CN103396828 B CN 103396828B
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Abstract
The invention discloses a polyether crude oil demulsifier using straight chain alkyl phenolic resin as an initiator and a preparation method and application thereof. The general formula of the polyether crude oil demulsifier using straight chain alkyl phenolic resin as an initiator is A-(PO)a-(PO)b-(EO)c-(PO)m, wherein PO is -(CH2-O-CH2CH2)-, EO is -(O-CH2CH2)-, A is shown in the description, and R are straight chain alkyls with carbon number of 6, n is an integer of 5-13, a is equal to m, and in the general formula, the mass of EO accounts for 15-25% of the mass sum of EO and PO. The polyether crude oil demulsifier prepared by the invention is simple in preparation process, good in surface activity, strong in demulsification capability and diffusion capability, good in dehydration effect, especially excellent in capability of perfecting oil-water interface emulsification performance and strong in universality, and the demulsification and dehydration rate of the crude oil reaches to 80-92%.
Description
Technical field
What the present invention relates to is emulsion splitter for eliminating Oil extraction smelting process Crude Oil emulsified state, is specifically the polyether crude oil demulsifier of initiator, its preparation method and application thereof with straight chain alkyl phenolic resin.
Background technology
In recent years along with the development of petroleum industry, particularly due to the application of intensification flooding oil recovery technique, especially thermal recovery technology, the water content of crude oil emulsion obviously increases.In prior art, at secondary oil recovery later stage and tertiary phase, implement the multiple well stimulations such as acidifying, pressure break, water blockoff, profile control, the injection of the various chemical displacement of reservoir oil and the raising of viscous crude ratio, what Produced Liquid also became becomes increasingly complex.The emulsion splitter of some routines can not meet the crude oil demulsification needs day by day changed.Diffusion and breakdown of emulsion ability are two leading indicators of reflection emulsion splitter performance quality.
Water in oil field produced crude oil and crude oil, can form milk sap under the effect of naturally occurring emulsifying agent, and these water-oil emulsions are in exploitation with collect through again stirring in defeated process, can disperse further, finally define stable crude oil emulsion.Along with field produces enters high water-cut stage, and large, the heavy various crude oil with poor quality ginseng refining ratio of various peracid, high-sulfur, viscosity is more and more higher, emulsification of crude oil phenomenon is on the rise, existing emulsion splitter much can not adapt to current breakdown of emulsion requirement, domestic existing emulsion splitter also exists following shortcoming more: the breakdown of emulsion ability universality of single emulsion splitter is poor, decline for current crude oil situation breakdown of emulsion ability, the consumption of emulsion splitter strengthens gradually, in order to tackle these situations, wide in the urgent need to developing a kind of universality, breakdown of emulsion ability is strong, the emulsion splitter that consumption is few.
Summary of the invention
The object of this invention is to provide a kind of take straight chain alkyl phenolic resin as the polyether crude oil demulsifier of initiator, its preparation method and application thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Take straight chain alkyl phenolic resin as a polyether crude oil demulsifier for initiator, its general formula is A-(PO)
a-(PO)
b-(EO)
c-(PO)
m, wherein PO is-(CH
2-O-CH
2cH
2)-, EO is-(O-CH
2cH
2)-, A is
the straight chained alkyl of R to be carbon number be 6-10, n is the integer of 5-13, a+b=m, and the weight-average molecular weight of general formula is 2800 ~ 3500, in general formula the quality of EO be PO and EO quality and 15%-25%.
In the present invention, PO is propenyloxy group, and EO is vinyloxy group.
In order to strengthen demulsification, R to be carbon number be 9 straight chained alkyl.
In order to strengthen demulsification, in general formula the quality of EO be PO and EO quality and 15-25%, be preferably 15%, 20% or 25%.
In order to easy to prepare, ensure the demulsification of product, a kind of take straight chain alkyl phenolic resin as the method for the polyether crude oil demulsifier of initiator, comprises the following steps simultaneously:
(1) using straight chain alkyl phenolic resin as initiator, under alkaline catalysts, it is 115 ~ 155 DEG C in temperature, pressure is under the reaction conditions of 0.1 ~ 0.8MPa, passes into PO and carries out polyreaction, treats that still internal pressure reduces to zero, reaction terminates, obtain intermediate, wherein, the mass ratio that feeds intake of initiator and PO is 1:(300 ~ 510);
(2) by the intermediate of step (1) gained and alkaline catalysts, temperature 115 ~ 155 DEG C, under the reaction conditions of pressure 0.1 ~ 0.8MPa, first pass into PO and carry out polyreaction, be after zero until still internal pressure, passing into EO again and carry out polyreaction, is after zero until still internal pressure, finally carries out polyreaction passing into PO, be after zero until still internal pressure, polyreaction terminates, and discharging after dehydration, is able to the polyether crude oil demulsifier that straight chain alkyl phenolic resin is initiator.
In order to demulsification that is easy to prepare, that improve yield, ensure product simultaneously, in step (1), being prepared as of straight chain alkyl phenolic resin: will molten straight chained alkyl phenol be dried, under alkaline catalysts, temperature is at 50 DEG C-80 DEG C, the formaldehyde solution of slow dropping 37%, the mol ratio of straight chained alkyl phenol and formaldehyde is 1:(0.8-1.5); After formaldehyde solution drips, be warming up to 100 DEG C-120 DEG C, reaction 1.5-2.0h, then be-0.08Mpa ~-0.1Mpa in vacuum tightness, under temperature is the condition of 145 DEG C ~ 155 DEG C, after dehydration 2 ~ 3h, obtain straight chain alkyl phenolic resin.
In order to improve demulsification further, straight chained alkyl phenol is straight chain nonyl phenol.
Conveniently be easy to get, improve speed of reaction simultaneously, ensure product performance; Step (1) and step (2) alkaline catalysts used are potassium hydroxide or sodium hydroxide, and consumption is with reference to prior art.
In order to improve demulsification further, above-mentioned take straight chain alkyl phenolic resin as the application of the polyether crude oil demulsifier of initiator.
Above-mentioned application preferably by take straight chain alkyl phenolic resin as the polyether crude oil demulsifier of initiator, heavy aromatics and methyl alcohol is (4 ~ 6) according to mass ratio: (3.5 ~ 5.5): the ratio mixing of (0.5 ~ 1.5), obtain emulsion splitter solution, then emulsion splitter solution is joined breakdown of emulsion in crude oil.
In order to ensure demulsification, simultaneously cost-saving, the add-on of emulsion splitter solution is 5-15ppm, and breakdown of emulsion temperature is 120-145 DEG C, and the breakdown of emulsion time is 8-25min.
The not specified technology of the present invention is prior art.
Polyether demulsification agent preparation technology prepared by the present invention is simple, good surface activity, breakdown of emulsion ability and diffusibility strong, have good dehydrating effect, crude oil demulsification dehydration rate reaches 80 ~ 92%, is especially improving performance excellence on water-oil interface emulsifying property, in the breakdown of emulsion experiment that the emulsion splitter using the present invention to prepare carries out, the clear consolidation of water-oil interface, aqueous phase is limpid, there is not water-oil interface emulsion.By to Pai Ruinisi crude oil, Shengli crude, Russian oil, Wei Yazi crude oil, Da Er crude oil, Daqing crude oil etc. carry out breakdown of emulsion experiment, all obtain good breaking emulsion and dewatering result, sufficient proof emulsion splitter of the present invention has very strong universality.
Accompanying drawing explanation
Fig. 1 is the molecular weight spectrogram of embodiment 3 gained polyethers;
Fig. 2 is the gel chromatography analysis of spectra of embodiment 3 gained polyethers;
The infrared spectrogram of Fig. 3 embodiment 3 gained polyethers.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
In product the quality PO of EO and EO quality and 15%:
(1) synthesis of initiator nonylphenolic resin
Adding in glass there-necked flask by drying molten nonyl phenol 190g, stirring, adding potassium hydroxide 1g, control temperature slowly drips the formaldehyde solution 150g of 37% at 50 DEG C ~ 80 DEG C; After adding formaldehyde solution, be warming up to 100 DEG C ~ 120 DEG C, 1.5 ~ 2.0 times of reaction, then after the 2 ~ 3h that dewaters under vacuum tightness-0.08Mpa ~-0.1Mpa and 145 DEG C ~ 155 DEG C conditions, cooling, discharging.
(2) synthesis of intermediate
The initiator 200g of step (1) gained and catalyzer KOH33g is dropped in autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gathers and meet PO10200g.
(3) synthesis of polyethers
By the intermediate 40g of step (2) gained and catalyzer KOH3.2g, drop in 1L autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gather and meet PO215g, then gather and meet EO90g, and then poly-meeting PO255g, discharging after dehydration, obtains polyethers.
Embodiment 2
In product the quality of EO be PO and EO quality and 20%:
The intermediate 40g synthesize step (2) in embodiment 1 and catalyzer KOH3.2g, drops in 1L autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gather and meet PO200g, then gather and meet EO120g, and then poly-meeting PO240g, discharging after dehydration, obtains polyethers.
Embodiment 3
In product the quality of EO be PO and EO quality and 25%:
By step (2) synthetic intermediate 40g and catalyzer KOH3.2g in embodiment 1, drop in 1L autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gather and meet PO185g, then gather and meet EO150g, and then poly-meeting PO225g, discharging after dehydration, obtains polyethers.
Embodiment 4
In product the quality of EO be PO and EO quality and 15%:
By step (2) synthetic intermediate 20g and catalyzer KOH3.2g in embodiment 1, drop in 1L autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gather and meet PO205g, then gather and meet EO90g, and then poly-meeting PO255g, discharging after dehydration, obtains polyethers.
Embodiment 5
In product the quality PO of EO and EO quality and 15%:
(1) synthesis of intermediate
The initiator 200g of step (1) gained in embodiment 1 and catalyzer KOH33g is dropped in autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gathers and meet PO6000g.
(2) synthesis of polyethers
By the intermediate 40g of step (2) gained and catalyzer KOH3.2g, drop in 1L autoclave, temperature 115 ~ 155 DEG C, under the condition of reaction pressure 0.1 ~ 0.8MPa, gather and meet PO215g, then gather and meet EO90g, and then poly-meeting PO255g, discharging after dehydration, obtains polyethers.
Above-described embodiment 1-5 gained polyethers the experiment condition of gel chromatography analysis of spectra be:
Column temperature: 25 DEG C; Solvent: THF (HPLC); Flow velocity: 1ml/min; HPLC pump: Waters515; Detector: RI:WyattOptilabrEX; Chromatographic column: HR3, HR4 and HR5Styagel chromatographic column three series connection; Standard specimen: PS(
=900 ~ 1.74 × 106g/mol, D<1.1).
Experimental result: the weight-average molecular weight of embodiment 3 products therefrom is 5800g/mol, the weight-average molecular weight of embodiment 4 products therefrom is 9200g/mol.The weight-average molecular weight of embodiment 1,2,5 products therefrom is all in 5000 ~ 10000.
Static dehydration experiment is carried out to the product of above-described embodiment 1-3, respectively by the polyether crude oil demulsifier of above-described embodiment gained and C10 heavy aromatics, methyl alcohol mixes according to the ratio of 4:5:1, obtain emulsion splitter solution, in crude oil emulsion, add this emulsion splitter solution fully mix, constant temperature standing sedimentation dewaters, record different time dehydrating amount, observe color and the water-oil interface situation of sewage, wherein the consumption of emulsion splitter is 10ppm, with crude oil emulsion sample quality for benchmark, from dewatering speed, dehydration rate, deviate from water quality, the performance of the aspect comprehensive evaluation synthesis emulsion splitters such as water-oil interface.Detect the use properties of emulsion splitter prepared by the present invention with this, specific experiment method is with reference to SY/T5281-2000, and get water solution of oil 100ml and test, experimental result is in table 1.
As can be seen from Table 1, the emulsion splitter that the present invention relates to is applied to multiple crude oil all stronger demulsification, and universality is good, dehydration rate is up to 80 ~ 92%, and water-oil interface do not exist emulsification substantially, there is the clear consolidation of water-oil interface, the advantages such as aqueous phase degree of cleaning are good.
The static dehydration experiment result of table 1 embodiment product
Claims (9)
1. be a polyether crude oil demulsifier for initiator with straight chain alkyl phenolic resin, it is characterized in that: its general formula is A-(PO)
a-(PO)
b-(EO)
c-(PO)
m, wherein PO is-(CH
2-O-CH
2cH
2)-, EO is-(O-CH
2cH
2)-, A is
the straight chained alkyl of R to be carbon number be 6-10, n is the integer of 5-13, a+b=m, and the weight-average molecular weight of general formula is 5000 ~ 10000, in general formula the quality of EO be PO and EO quality and 15%-25%.
2. as claimed in claim 1 take straight chain alkyl phenolic resin as the polyether crude oil demulsifier of initiator, it is characterized in that: R to be carbon number be 9 straight chained alkyl.
3. as claimed in claim 2 take straight chain alkyl phenolic resin as the polyether crude oil demulsifier of initiator, it is characterized in that: in general formula the quality of EO be PO and EO quality and 15%, 20% or 25%.
4. preparing described in claim 1-3 any one take straight chain alkyl phenolic resin as the method for the polyether crude oil demulsifier of initiator, it is characterized in that: comprise the following steps:
(1) using straight chain alkyl phenolic resin as initiator, under alkaline catalysts, it is 115 ~ 155 DEG C in temperature, pressure is under the reaction conditions of 0.1 ~ 0.8MPa, passes into PO and carries out polyreaction, after still internal pressure reduces to zero, reaction terminates, obtain intermediate, wherein, the mass ratio that feeds intake of initiator and PO is 1:(30 ~ 51);
(2) by the intermediate of step (1) gained and alkaline catalysts, temperature 115 ~ 155 DEG C, under the reaction conditions of pressure 0.1 ~ 0.8MPa, first pass into PO and carry out polyreaction, be after zero until still internal pressure, pass into EO again and carry out polyreaction, be after zero until still internal pressure, finally pass into PO again and carry out polyreaction, be after zero until still internal pressure, polyreaction terminates, and discharging after dehydration, is able to the polyether crude oil demulsifier that straight chain alkyl phenolic resin is initiator;
In above-mentioned steps (1) and (2), lead to EO quality be PO and EO quality and 15%-25%, in the PO quality passed in step (1) and step (2) first time the PO quality that passes into and equal the PO quality that step (2) second time passes into.
5. method as claimed in claim 4, it is characterized in that: in step (1), being prepared as of straight chain alkyl phenolic resin: will molten straight chained alkyl phenol be dried, under alkaline catalysts, temperature is at 50 DEG C ~ 80 DEG C, the formaldehyde solution of slow dropping 37%, the mol ratio of straight chained alkyl phenol and formaldehyde is 1:(0.8 ~ 1.5); After formaldehyde solution drips, be warming up to 100 DEG C ~ 120 DEG C, reaction 1.5 ~ 2.0h, then be-0.08Mpa ~-0.1Mpa in vacuum tightness, under temperature is the condition of 145 DEG C ~ 155 DEG C, after dehydration 2 ~ 3h, obtain straight chain alkyl phenolic resin.
6. the method as described in claim 4 or 5, is characterized in that: straight chained alkyl phenol is straight chain nonyl phenol; In step (1) and step (2), alkaline catalysts used is potassium hydroxide or sodium hydroxide.
7. described in claim 1-3 any one take straight chain alkyl phenolic resin as the application of the polyether crude oil demulsifier of initiator.
8. be the application of the polyether crude oil demulsifier of initiator as claimed in claim 7 with straight chain alkyl phenolic resin, it is characterized in that: by take straight chain alkyl phenolic resin as the polyether crude oil demulsifier of initiator, heavy aromatics and methyl alcohol is (4 ~ 6) according to mass ratio: (3.5 ~ 5.5): the ratio mixing of (0.5 ~ 1.5), obtain emulsion splitter solution, then emulsion splitter solution is joined breakdown of emulsion in crude oil.
9. be the application of the polyether crude oil demulsifier of initiator as claimed in claim 8 with straight chain alkyl phenolic resin, it is characterized in that: the add-on of emulsion splitter solution is 5-15ppm, and breakdown of emulsion temperature is 120-145 DEG C, and the breakdown of emulsion time is 8-25min.
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| CN104231197B (en) * | 2014-09-05 | 2016-07-13 | 中国海洋石油总公司 | A kind of amino modified phenolic resin and preparation method thereof |
| CN105440278B (en) * | 2015-12-31 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of demulsifier compound system and the preparation method and application thereof |
| CN106380591B (en) * | 2016-08-25 | 2018-04-20 | 金浦新材料股份有限公司 | A kind of oil product anti emulsifier |
| CN107841334B (en) * | 2017-11-28 | 2022-03-01 | 中国石油天然气集团公司 | Synthetic method of novel crude oil demulsifier suitable for complex incoming liquid |
| CN110387256B (en) * | 2018-04-23 | 2021-11-19 | 盘锦富隆化工有限公司 | Low-temperature rapid demulsifier for polymer flooding crude oil and preparation method thereof |
| CN110791310A (en) * | 2018-08-02 | 2020-02-14 | 中国石油化工股份有限公司 | Demulsifier for dehydrating heavy oil in oil field and preparation method thereof |
| CN110923003B (en) * | 2019-11-01 | 2021-07-20 | 德仕能源科技集团股份有限公司 | Preparation method of demulsifier for high-wax-content crude oil with wax content of not less than 20% |
| CN110734543B (en) * | 2019-11-11 | 2022-04-29 | 煤炭科学技术研究院有限公司 | Naphthol modified phenolic resin and preparation method and application thereof |
| CN111154055A (en) * | 2020-01-20 | 2020-05-15 | 金浦新材料股份有限公司 | Synthetic method of special initiator for polyether crude oil demulsifier |
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| CN101352667B (en) * | 2007-07-26 | 2010-08-25 | 中国石油化工股份有限公司 | Demulsifying agent and preparation method and use thereof |
| CN101220144A (en) * | 2008-01-24 | 2008-07-16 | 中国石油技术开发公司 | Modified synergistic method of multi-block polyether |
| CN103011337A (en) * | 2012-10-30 | 2013-04-03 | 中国石油化工股份有限公司 | Polymer flooding produced liquid polymer retaining comprehensive treatment agent and application method |
| CN102925204B (en) * | 2012-10-30 | 2014-12-03 | 中国石油化工股份有限公司 | Foam combination flooding produced liquid demulsifier and preparation method thereof |
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