CN101717518A - Preparation method and application of block polyether-beta-CD comb type demulsifying agent - Google Patents
Preparation method and application of block polyether-beta-CD comb type demulsifying agent Download PDFInfo
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- CN101717518A CN101717518A CN200910216169A CN200910216169A CN101717518A CN 101717518 A CN101717518 A CN 101717518A CN 200910216169 A CN200910216169 A CN 200910216169A CN 200910216169 A CN200910216169 A CN 200910216169A CN 101717518 A CN101717518 A CN 101717518A
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Abstract
The invention relates to a preparation method and an application of a block polyether-beta-CD comb type demulsifying agent for demulsifying and dewatering crude oil. The invention can improve the demulsifying and dewatering efficiency of a crude oil demulsifying agent and the molecular weight and the compounding capacity of the demulsifying agent. The preparation method comprises the following steps of: dissolving beta-cyclodextrin in dimethysulfoxide (DMSO), using NaOH as a catalyst and slowly dropping allylbromide to react for 48 hours at a temperature of 0-10 DEG C to obtain allyl-beta-cyclodextrin; dissolving the allyl-beta-cyclodextrin and acrylic acid raw materials in water, and under the protection of nitrogen, carrying out a polymerization reaction for 8 hours by using NaHSO3 and (NH4)2S2O7 as an initiating system so as to obtain a cyclodextrin/acrylic acid main chain polymer; and finally, putting the main chain polymer and polyoxy-ethylene block polyether in a reactor to react for 12-16 hours to obtain a product, and extracting and centrifugally separating the product to obtain the block polyether-beta-CD comb type demulsifying agent. The preparation method has simple operation, moderate condition, simple equipment and easy industrial production. After the block polyether-beta-CD comb type demulsifying agent is mixed with crude oil, the water yield of the crude oil is high, and the demulsifying time is short, thus the block polyether-beta-CD comb type demulsifying agent can be widely applied to oil fields and refineries for demulsifying and dewatering.
Description
Technical field
The present invention relates to a kind of preparation method and application that is used for the block polyether-β-CD comb type demulsifying agent of field breaking emulsion and dewaterings such as oil field, refinery, be specially adapted to the breakdown of emulsion of oil field produced O/W and w/o type crude oil.
Background technology
The breaking emulsion and dewatering of crude oil emulsion is an important step of petroleum production processes process.Because most of oilfield exploitation of China enters the middle and later periods, inject increasing of water and make the water ratio height of extraction oil, and emulsion system is more complicated stable, interfacial film intensity increases, and makes the demulsification reduction.
The most frequently used crude oil demulsification method promptly is to add emulsion splitter in crude oil in the petroleum industry at present.The emulsion splitter of domestic present use still is traditional oxyethane propylene oxide block copolyether, but its demulsification has begun to satisfy the production needs, so the exploitation of novel emulsion splitter is inevitable.Wherein, the breakdown of emulsion of ultra-high molecular weight because of it has that consumption is low, breakdown of emulsion efficient height, to characteristics such as various crude oil emulsion wide adaptabilities, be the developing direction of current emulsion splitter, have good prospect.
In addition, the synergy breakdown of emulsion of emulsion splitter and composite dose also is the important method that improves breakdown of emulsion efficient.But composite dose selection is subjected to the influence of emulsion system and has limitation, influenced by system, and composite effect can't reach optimum regime.
Summary of the invention
The objective of the invention is: in order to improve the breaking emulsion and dewatering efficient of crude oil demulsifier, improve the molecular weight and the compounding capacity of emulsion splitter, adopting allyl group-β-CD/ vinylformic acid is that main chain, block polyether are side chain, to existing main body inclusion function, have the main chain of higher molecular weight to carry out branching again, the spy provides the preparation method and the application of a kind of block polyether-β-CD comb type demulsifying agent.
For achieving the above object, the present invention is by the following technical solutions: earlier 4～6mmol beta-cyclodextrin is dissolved in 25～40ml dimethyl sulfoxide (DMSO) (being labeled as DMSO) solvent, place the there-necked flask that has stirring rake, add 2～3gNaOH as catalyzer, slowly drip 8～9ml bromopropylene down at 0～10 ℃, the mol ratio of bromopropylene and beta-cyclodextrin is 1: 1.6～1: 3, stirring reaction 45～50h under the normal temperature, to precipitating 3～5 times with washing with acetone behind the product vacuum filtration, promptly make the allyl group-beta-cyclodextrin; Structural formula is as follows:
Wherein
Be beta-cyclodextrin
Again the above-mentioned allyl group-beta-cyclodextrin that makes is added vinylformic acid, its mol ratio is 1: 0.5～1: 3, be dissolved in the distilled water, under nitrogen protection, mixed system with sodium bisulfite and ammonium persulphate mass ratio 1: 1 (is unit with the gram) is an initiator system, and polyreaction 7～10h under the normal temperature obtains white transparent jelly, with obtaining white solid matter behind the absolute ethanol washing, 80 ℃ get allyl group-β-CD/ propenoic acid main chain polymkeric substance after drying, the pulverizing down; Structural formula is as follows:
Wherein the molar percentage of x is 5～12%
At last the above-mentioned allyl group-β that makes-CD/ propenoic acid main chain polymkeric substance is added the polyoxyethylene polyoxypropylene block polyether, its mol ratio is that mixing in 1: 1～1: 1.5 places esterifier, add again and account for the tosic acid solid of total mass 1.2% as catalyzer, the cyclohexane give that accounts for total mass 12% is the band aqua, at 120～140 ℃ of following esterification 12～16h, the extraction of product water, centrifugation, promptly make block polyether-β of the present invention-CD comb type demulsifying agent product, be labeled as β-CD-D.Structural formula is as follows:
M=2～60 wherein, n=15～80
The described polyoxyethylene polyoxypropylene block polyether of preparation method of the present invention is the commercially available prod, is to be initiator with propylene glycol, ethylene glycol, with the diblock or the multi-block polyether of oxyethane, propylene oxide polymerization system.
A kind of block polyether-β-the application of CD comb type demulsifying agent in crude oil demulsification, earlier block polyether-β-CD comb type demulsifying agent is dissolved in and is mixed with the emulsion splitter solution that mass concentration is 0.01g/mL～0.1g/mL in the dimethylbenzene, adding 10%NaOH adjusting pH value to 6～8; Emulsion splitter solution is joined in the crude oil, the emulsion splitter consumption is to add 100～300 μ g in every gram crude oil again; The breakdown of emulsion temperature is 30～80 ℃; The breakdown of emulsion time is 60～150min; The crude oil demulsification dehydration rate reaches 80～95%.
Compared with prior art, the present invention has following beneficial effect:
(1) adopting the allyl group-beta-cyclodextrin is one of main chain polymeric monomer, not only can improve the molecular weight of emulsion splitter, has introduced the cyclodextrin with main functionality simultaneously, makes it have better composite effect; (2) emulsion splitter preparation method of the present invention is simple, mild condition, and equipment is simple, is easy to suitability for industrialized production; (3) emulsion splitter molecular weight of the present invention is big, is a kind of emulsion splitter of polymer efficiently, has many neat side chains, can use and various types of crude oil demulsifications, easy to operate, can bigger raising breakdown of emulsion efficient, can be widely used in the breaking emulsion and dewatering of oil field, refinery etc.
Embodiment
Below by specific examples the present invention is further detailed.
Example 1
Getting beta-cyclodextrin 5.7mmol adding has in the there-necked flask of constant voltage titration funnel, stirring rake, add 30ml DMSO again, 2.0gNaOH, fully stirring 1h dissolves cyclodextrin fully, slow dripping bromine propylene 8ml in 0～10 ℃ of water-bath continues isothermal reaction 48h then, reaction finish the back with vacuum filtration, and use washing with acetone, obtain white powder, make the allyl group-beta-cyclodextrin.
Be raw material with allyl group-beta-cyclodextrin and vinylformic acid again, pressed material molar ratio 1: 2, in the aqueous solution under 60 ℃, add sodium bisulfite and 1: 1 mixed system of ammonium persulphate mass ratio as initiator, constant temperature polyreaction 8h, react and finish the back, obtain allyl group-beta-cyclodextrin/propenoic acid main chain polymkeric substance after drying, the pulverizing with the absolute ethanol washing precipitation.
Take by weighing the above-mentioned trunk polymer of 15g at last, 22.5g polyoxyethylene polyoxypropylene block polyether, 5ml distilled water is in esterifier, adding the 8ml cyclohexane give is esterification band aqua, fully stir and be warming up to 140 ℃, add the 0.6g tosic acid as catalyzer, isothermal reaction 12h, steam hexanaphthene band aqua and part residual water after having reacted, obtain the yellowish brown thick liquid.Be labeled as β-CD-D-1.
Example 2
Get beta-cyclodextrin 5.7mmol in the there-necked flask that has constant voltage titration funnel, stirring rake, add 30ml DMSO again, 2.0gNaOH, fully stirring 1h dissolves cyclodextrin fully, slow dripping bromine propylene 8ml in 0～10 ℃ of water-bath continues isothermal reaction 48h then, reaction finish the back with vacuum filtration, and use washing with acetone, obtain white powder, make the allyl group-beta-cyclodextrin.
Be raw material with allyl group-beta-cyclodextrin and vinylformic acid again, pressed material molar ratio 1: 1, in the aqueous solution under 60 ℃, add sodium bisulfite and 1: 1 mixed system of ammonium persulphate mass ratio as initiator, constant temperature polyreaction 8h, react and finish the back, obtain allyl group-beta-cyclodextrin/propenoic acid main chain polymkeric substance after drying, the pulverizing with the absolute ethanol washing precipitation.
Take by weighing the above-mentioned trunk polymer of 15g at last, 15g polyoxyethylene polyoxypropylene block polyether, 5ml distilled water is in esterifier, adding the 8ml cyclohexane give is esterification band aqua, fully stir and be warming up to 140 ℃, add the 0.6g tosic acid as catalyzer, isothermal reaction 12h, steam hexanaphthene band aqua and part residual water after having reacted, obtain the yellowish brown thick liquid.Be labeled as β-CD-D-2.
Example 3
Get beta-cyclodextrin 5.7mmol in the there-necked flask that has constant voltage titration funnel, stirring rake, add 30ml DMSO again, 2.0gNaOH, fully stirring 1h dissolves cyclodextrin fully, slow dripping bromine propylene 8ml in 0～10 ℃ of water-bath continues isothermal reaction 48h then, reaction finish the back with vacuum filtration, and use washing with acetone, obtain white powder, make the allyl group-beta-cyclodextrin.
Be raw material with allyl group-beta-cyclodextrin and vinylformic acid again, pressed material molar ratio 1: 0.5, in the aqueous solution under 60 ℃, add sodium bisulfite and 1: 1 mixed system of ammonium persulphate mass ratio as initiator, constant temperature polyreaction 8h, react and finish the back, obtain allyl group-beta-cyclodextrin/propenoic acid main chain polymkeric substance after drying, the pulverizing with the absolute ethanol washing precipitation.
Take by weighing the above-mentioned trunk polymer of 15g at last, 7.5g polyoxyethylene polyoxypropylene block polyether, 5ml distilled water is in esterifier, adding the 8ml cyclohexane give is esterification band aqua, fully stir and be warming up to 140 ℃, add the 0.6g tosic acid as catalyzer, isothermal reaction 12h, steam hexanaphthene band aqua and part residual water after having reacted, obtain the yellowish brown thick liquid.Be labeled as β-CD-D-3.
Example 4: crude oil demulsification experiment
Adopt oil and gas industry standard SY/T5281-2000, crude oil demulsifier use properties detection method (bottle examination method) is tested the demulsification of this emulsion splitter, and experiment crude oil is Liaohe Oil Field collection output oil, viscosity 80mPss (25 ℃), water ratio 27%.The used emulsion splitter of control experiment is that TA1031, SP-169 buy from grand magnificent petrochemical complex company limited of Fushun Jiahua Chemicals Co., Ltd, Jingzhou City respectively.It is as follows to obtain experimental result:
Claims (3)
1. the preparation method of block polyether-β-CD comb type demulsifying agent, it is characterized in that: earlier 4～6mmol beta-cyclodextrin is dissolved in 25～40ml dimethyl sulfoxide solvent, place the there-necked flask that has stirring rake, add 2～3gNaOH as catalyzer, slowly drip 8～9ml bromopropylene down at 0～10 ℃, the mol ratio of bromopropylene and beta-cyclodextrin is 1: 1.6～1: 3, stirring reaction 45～50h under the normal temperature, to precipitating 3～5 times with washing with acetone behind the product vacuum filtration, promptly make the allyl group-beta-cyclodextrin; Again the above-mentioned allyl group-beta-cyclodextrin that makes is added vinylformic acid, its mol ratio is 1: 0.5～1: 3, be dissolved in the distilled water, under nitrogen protection, with sodium bisulfite and 1: 1 mixed system of ammonium persulphate mass ratio is initiator system, and polyreaction 7～10h under the normal temperature obtains white transparent jelly, with obtaining white solid matter behind the absolute ethanol washing, 80 ℃ get allyl group-β-CD/ propenoic acid main chain polymkeric substance after drying, the pulverizing down; At last the above-mentioned allyl group-β that makes-CD/ propenoic acid main chain polymkeric substance is added the polyoxyethylene polyoxypropylene block polyether, its mol ratio is that mixing in 1: 1～1: 1.5 places esterifier, add again and account for the tosic acid solid of total mass 1.2% as catalyzer, the cyclohexane give that accounts for total mass 12% is the band aqua, at 120～140 ℃ of following esterification 12～16h, the extraction of product water, centrifugation promptly make this block polyether-β-CD comb type demulsifying agent product.
2. the preparation method of emulsion splitter according to claim 1, it is characterized in that: described polyoxyethylene polyoxypropylene block polyether is the commercially available prod, be to be initiator, with the diblock or the multi-block polyether of oxyethane, propylene oxide polymerization system with propylene glycol, ethylene glycol.
3. block polyether-β-the application of CD comb type demulsifying agent in crude oil demulsification, it is characterized in that: elder generation is dissolved in block polyether-β-CD comb type demulsifying agent and is mixed with the emulsion splitter solution that mass concentration is 0.01g/mL～0.1g/mL in the dimethylbenzene, regulates pH value to 6～8 with 10%NaOH; Emulsion splitter solution is joined in the crude oil, the emulsion splitter consumption is to add 100～300 μ g in every gram crude oil again; The breakdown of emulsion temperature is 30～80 ℃; The breakdown of emulsion time is 60～150min; The crude oil demulsification dehydration rate reaches 80～95%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194822A (en) * | 2014-09-04 | 2014-12-10 | 中国海洋石油总公司 | Cross-linked nonionic polyether crude oil demulsifier and preparation method thereof |
| CN113583190A (en) * | 2021-07-12 | 2021-11-02 | 武汉理工大学 | 4-tert-butylcalix [4] arene modified polycarboxylic acid water reducer and preparation method thereof |
| CN113667055A (en) * | 2021-07-21 | 2021-11-19 | 西南石油大学 | Acrylate-polymerizable quaternary ammonium salt copolymer demulsifier and preparation method thereof |
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| CN102924670B (en) * | 2012-11-01 | 2014-10-01 | 天津大学 | Synthesis and application of novel cyclodextrin polymer chiral resolving agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194822A (en) * | 2014-09-04 | 2014-12-10 | 中国海洋石油总公司 | Cross-linked nonionic polyether crude oil demulsifier and preparation method thereof |
| CN104194822B (en) * | 2014-09-04 | 2015-11-18 | 中国海洋石油总公司 | A kind of cross-linking type nonionic polyoxyalkylene crude oil demulsifier and preparation method thereof |
| CN113583190A (en) * | 2021-07-12 | 2021-11-02 | 武汉理工大学 | 4-tert-butylcalix [4] arene modified polycarboxylic acid water reducer and preparation method thereof |
| CN113667055A (en) * | 2021-07-21 | 2021-11-19 | 西南石油大学 | Acrylate-polymerizable quaternary ammonium salt copolymer demulsifier and preparation method thereof |
| CN113667055B (en) * | 2021-07-21 | 2022-09-02 | 中海油(天津)油田化工有限公司 | Acrylate-polymerizable quaternary ammonium salt copolymer demulsifier and preparation method thereof |
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