CN102432888B - Comb-shaped polysiloxane crude-oil demulsifying agent and preparation method thereof - Google Patents
Comb-shaped polysiloxane crude-oil demulsifying agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a comb-shaped polysiloxane crude-oil demulsifying agent and a preparation method thereof. The invention is modified by silicon oil, and by hydrosilation reaction, crylic-acid polyoxyethylene polyoxypropylene ester, methacrylic acid and acrylate are respectively connected onto linear polysiloxane of the silicon oil. The comb-shaped polysiloxane crude-oil demulsifying agent provided by the invention not only can reduce the tension and the strength of an oil-water interface, but also has good hydrophilic capability and oleophylic capability, so that a product is applicable to oil-in-water type crude oil emulsion and water-in-oil type crude oil emulsion and has the advantages of less use amount, fast water distribution, low demulsification temperature, wide application range and the like.
Description
Technical field
The invention belongs to the emulsion splitter that dehydrating of crude oil is processed, relate to a kind of comb type polysiloxane crude oil demulsifier and preparation method thereof.
Background technology
Crude oil demulsifier is to implement dehydrating of crude oil to process the chemical reagent of using.That uses at present mainly has amine, alcohols, alkyl phenolic resin class, phenol amine aldehyde resin class, the serial emulsion splitter of polysiloxane-based polyoxyethylene poly-oxygen propylene aether as initiator and composite product and a polymer type crude oil demulsifier.
Recover the oil the stage along with the exploitation in each oil field has entered the later stage in succession, the continuous application of various oil field chemicals makes crude oil demulsification more and more difficult.In addition, because the local geographical environment of difference is different, the composition difference of crude oil is very large, requirement to crude oil demulsifier is not identical yet, existing crude oil demulsifier breakdown of emulsion ability can not satisfy current needs, therefore is badly in need of a kind of breakdown of emulsion ability of exploitation strong, the Novel crude oil demulsifier that suitability is wide.
Application number is that 02138900.4 Chinese patent discloses a kind of broad spectrum type crude oil demulsifier, with polynary polyethers, polyamine polyethers and the composite enhancing emulsion splitter of pour point depressant adaptability.Application number is that 98113742.3 Chinese patent discloses a kind of crude oil demulsifier and preparation method thereof, makes oxyethane, propylene oxide block polyethers take ethylene glycol or propylene glycol as initiator and must adapt to the emulsion splitter of viscous crude with multi isocyanate crosslinking.Application number is that 98113741.5 Chinese patent discloses a kind of polymer type crude oil demulsifier, form polymer type crude oil demulsifier and the viscous crude affinity is good with the copolymerization by a certain percentage of vinylbenzene, methyl methacrylate, methyl acrylate, butyl acrylate, Isooctyl acrylate monomer, vinylformic acid and methacrylic acid, have good breaking emulsion and dewatering effect.Application number is the preparation that 200910113488.8 Chinese patent discloses a kind of organic silicon petroleum de-emulsifier, reacts to get crude oil demulsifier with organic silicon polyether and tolylene diisocyanate, can reduce oil water interfacial tension and interfacial film intensity.
Summary of the invention
The problem that the present invention solves is to provide a kind of comb type polysiloxane crude oil demulsifier and preparation method thereof, has a consumption few, and minute water is fast, and the breakdown of emulsion temperature is low, advantage applied widely.
The present invention is achieved through the following technical solutions:
A kind of comb type polysiloxane crude oil demulsifier, its structural formula is as follows:
In formula: R
1Be propylene-glycol-based, octadecanol base, tetramethylolmethane base, quadrol base, alkyl phenolic resin base, polyethylene polyamine base, phenol amine aldehyde radical;
R2 is methyl methacrylate base, styryl, butyl acrylate base, Isooctyl acrylate monomer base;
Wherein, n=1～50; X=1～20; Y=1～50; Z=1～30; A=20～50; B=30～60.
A kind of preparation method who combs type polysiloxane crude oil demulsifier comprises the following steps:
1) in molfraction, add the containing hydrogen silicone oil of S part in reaction solvent, and to add catalyzer Platinic chloride to concentration be 60～120ppm, the reactant that then adds T part carries out hydrosilation reaction at 80～120 ℃, and the reaction times is 6～10h;
Described reactant is according to vinylformic acid polyoxyethylene polyoxypropylene ester: the mixture that the mol ratio of methacrylic acid: methacrylic ester=x: y: z is mixed the three, x=1～20, y=1～50, z=1～30; S: T=1: 1～1.2;
2) after hydrosilation reaction is completed, reaction product with extracting dissolution with solvents, is regulated pH to neutral, shake up rear standing demix, collect the layer that comprises reaction product, remove and extract solvent, obtain comb type polysiloxane crude oil demulsifier.
Described reaction solvent is Virahol, and the extraction solvent is methylene dichloride.
In massfraction, the hydrogen content of described containing hydrogen silicone oil is 0.1～0.25%.
Described vinylformic acid polyoxyethylene polyoxypropylene ester is vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester, vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester, vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester, vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester, vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester, acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester or vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester.
Being prepared as of described vinylformic acid polyoxyethylene polyoxypropylene ester:
A kind of and vinylformic acid in propylene glycol polyoxyethylene poly-oxygen propylene aether, alkyl phenolic resin polyoxyethylene poly-oxygen propylene aether, polyethylene polyamine polyoxyethylene poly-oxygen propylene aether, ethylenediamine polyoxyethylene polyethenoxy ether, octadecanol polyoxyethylene polyoxypropylene, pentaerythritol polyoxyethylene poly-oxygen propylene aether, phenol amine aldehyde resin polyoxyethylene poly-oxygen propylene aether was mixed in 1: 1.2 in molar ratio, add again the toluenesulphonic acids of quality 2～6% after mixing and 0.6～1.2% Resorcinol, react 6h～8h under 120～145 ℃;
After question response is completed, reaction product is dissolved with methylene dichloride, regulate pH value to neutral with NaOH solution, shake up rear standing demix, tell subnatant, remove methylene dichloride, obtain vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester.
Described acrylate is methyl methacrylate, methyl acrylate, butyl acrylate, Isooctyl acrylate monomer or is vinylbenzene.
Described add containing hydrogen silicone oil and Platinic chloride in reaction solvent after, be heated to 80～120 ℃, in 1～2h, reactant is dripped, then continue reaction 4～8h at 80～120 ℃.
After described hydrosilation reaction is completed, reaction product is dissolved with methylene dichloride, then use NaHCO
3Solution is regulated pH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride, obtains comb type polysiloxane crude oil demulsifier.
Compared with prior art, the present invention has following useful technique effect:
Comb type polysiloxane crude oil demulsifier provided by the invention, it is the modification to silicone oil, pass through hydrosilation reaction, connect respectively vinylformic acid polyoxyethylene polyoxypropylene ester, methacrylic acid, acrylate on the linear polysiloxanes of silicone oil, and can according to the different requirements of different crude oils composition, by dehydration test, three's ratio be adjusted.
Further, for the requirement of different crude oils breakdown of emulsion, can adopt different types of vinylformic acid polyoxyethylene polyoxypropylene ester, acrylate and silicone oil to react.
Comb type polysiloxane crude oil demulsifier provided by the invention, can not only reduce oil water interfacial tension and boundary strength, and have good hydrophilic, an oleophylic ability, make product be applicable to oil-in-water-type crude oil emulsion and water-in-oil-type crude oil emulsion, has consumption few, the advantages such as minute water is fast, and the breakdown of emulsion temperature is low, and is applied widely.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment and result of use, and the explanation of the invention is not limited.
Comb type polysiloxane crude oil demulsifier provided by the invention, it is the modification to silicone oil, by hydrosilation reaction, connect respectively vinylformic acid polyoxyethylene polyoxypropylene ester, methacrylic acid, acrylate on the linear polysiloxanes of silicone oil, its structural formula is as follows:
In formula: R
1Be propylene-glycol-based, octadecanol base, tetramethylolmethane base, quadrol base, alkyl phenolic resin base, polyethylene polyamine base, phenol amine aldehyde radical;
R
2Be methyl methacrylate base, styryl, butyl acrylate base, Isooctyl acrylate monomer base;
Wherein, n=1～50; X=1～20; Y=1～50; Z=1～30; A=20～50; B=30～60.
Embodiment 1
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester
Take propylene glycol polyoxyethylene poly-oxygen propylene aether (molecular weight 2000) 20.00g, vinylformic acid 1.73g, catalyzer tosic acid 0.43g, hydroquinone of polymerization retarder 0.13g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 140 ℃, back flow reaction 6h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 14.12g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 110 ℃;
After claiming that prepared vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester 12.98g, methacrylic acid 1.06g, methyl methacrylate 1.25g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 110 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 110 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted methyl methacrylate with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier A.
Embodiment 2
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester, identical with embodiment 1
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 14.12g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 110 ℃;
After claiming that prepared vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester 12.98g, methacrylic acid 0.53g, methyl methacrylate 1.85g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 110 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 110 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted methyl methacrylate with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier B.
Embodiment 3
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester, identical with embodiment 1
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 14.12g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 110 ℃;
After claiming that prepared vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester 15.58g, methacrylic acid 1.70g, methyl methacrylate 0.25g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 110 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 110 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted methyl methacrylate with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier C.
Emulsion splitter for above-mentioned preparation, long celebrating Baota District crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is formed by long celebrating Baota District dewatered oil and sewage configuration), specifically with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have good dehydrating effect, and concrete outcome is as shown in table 1.
Table 1 comb type polysiloxane crude oil demulsifier is to long celebrating Baota District crude oil different time dehydration rate
Embodiment 4
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester
Take polyethylene polyamine polyoxyethylene poly-oxygen propylene aether (molecular weight 3000) 30.00g, vinylformic acid 0.87g, catalyzer tosic acid 0.61g, hydroquinone of polymerization retarder 0.19g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 145 ℃, back flow reaction 8h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 30.00g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 115 ℃;
After claiming that prepared vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester 37.66g, methacrylic acid 1.06g, butyl acrylate 1.58g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 115 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 115 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted butyl acrylate with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier D.
Emulsion splitter for above-mentioned preparation, long Qingan County plug district crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is formed by long Qingan County's plug district dewatered oil and sewage configuration), specifically with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have outstanding dehydrating effect, and concrete outcome is as shown in table 2.
Table 2 comb type polysiloxane crude oil demulsifier is to long Qingan County plug district crude oil different time dehydration rate
Emulsion splitter HQ96-1: clear industrial and trading company converges in Shaanxi; DB-2000 crude oil demulsifier, Shaanxi be nation's industry and trade company limited all
Embodiment 5
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester
Take alkyl phenolic resin polyoxyethylene poly-oxygen propylene aether (molecular weight 1500) 20.00g, vinylformic acid 1.12g, catalyzer tosic acid 0.43g, hydroquinone of polymerization retarder 0.13g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 135 ℃, back flow reaction 6h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 21.25g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 120 ℃;
After claiming that prepared acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester 19.17g, methacrylic acid 1.06g, Isooctyl acrylate monomer 2.27g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 120 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 120 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted Isooctyl acrylate monomer with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier E.
Emulsion splitter for above-mentioned preparation, long Qing Zichang district crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is configured by long Qing Zichang district's dewatered oil and sewage and forms), specifically with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have outstanding dehydrating effect, and concrete outcome is as shown in table 3.
Table 3 comb type polysiloxane crude oil demulsifier is to long Qing Zichang district crude oil different time dehydration rate
Emulsion splitter HQ96-1: clear industrial and trading company converges in Shaanxi; DB-2000 crude oil demulsifier, Shaanxi be nation's industry and trade company limited all
Embodiment 6
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester
Take vinylformic acid octadecanol polyoxyethylene poly-oxygen propylene aether (molecular weight 2500) 20.00g, vinylformic acid 0.70g, catalyzer tosic acid 0.41g, hydroquinone of polymerization retarder 0.13g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 130 ℃, back flow reaction 6h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 110 ℃;
After claiming that prepared vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester 31.50g, methacrylic acid 1.06g, vinylbenzene 1.29g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 110 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 110 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted vinylbenzene with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier F.
Emulsion splitter for above-mentioned preparation, long Qing Zichang district crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is configured by long Qing Zichang district's dewatered oil and sewage and forms), specifically with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have outstanding dehydrating effect, and dehydration rate reaches 91.7%
Embodiment 7
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester
Take vinylformic acid pentaerythritol polyoxyethylene poly-oxygen propylene aether (molecular weight 2200) 20.00g, vinylformic acid 0.79g, catalyzer tosic acid 0.41g, hydroquinone of polymerization retarder 0.14g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 135 ℃, back flow reaction 6h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 115 ℃;
After claiming that prepared vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester 27.80g, methacrylic acid 1.06g, vinylbenzene 1.29g mix, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 120 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 115 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted vinylbenzene with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier F.
Emulsion splitter for above-mentioned preparation, long Qing Zichang district crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is configured by long Qing Zichang district's dewatered oil and sewage and forms), specifically with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have outstanding dehydrating effect, and dehydration rate reaches 92.8%
Embodiment 8
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester
Take vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester ether (molecular weight 1800) 20.00g, vinylformic acid 0.96g, catalyzer tosic acid 0.42g, hydroquinone of polymerization retarder 0.14g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 135 ℃, back flow reaction 6h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 120 ℃;
Claim prepared vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester 22.87g, methacrylic acid 1.06g, Isooctyl acrylate monomer 2.27g, after mixing, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 120 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 120 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted Isooctyl acrylate monomer with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier G.
Emulsion splitter for above-mentioned preparation, long Qingan County plug district crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is formed by long Qing Zichang district's dewatered oil and sewage configuration), specifically compare with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have outstanding dehydrating effect, and dehydration rate reaches 89.6%
Embodiment 9
The preparation method of comb type polysiloxane crude oil demulsifier comprises the following steps:
1) preparation of vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester
Take vinylformic acid phenol amine aldehyde resin polyoxyethylene poly-oxygen propylene aether (molecular weight 2900) 20.00g, vinylformic acid 0.60g, catalyzer tosic acid 0.42g, hydroquinone of polymerization retarder 0.12g, add in the there-necked flask that agitator, water trap, spherical condensation tube, thermometer are housed, be heated to 135 ℃, back flow reaction 6h;
After reaction is completed, reactant is poured in pear shape separatory funnel, add methylene dichloride 50ml that it is dissolved fully, then regulate pH to neutral with the NaOH solution of 0.05mol/L, shake up rear standing demix, tell subnatant, steam methylene dichloride with Rotary Evaporators and namely get product vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm add in the four-hole boiling flask that dropping funnel, spherical condensation tube, thermometer, agitator are housed, and are heated to 120 ℃;
Claim prepared vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester 36.43g, methacrylic acid 1.06g, methyl methacrylate 1.25g, after mixing, the slow dropping of containing hydrogen silicone oil system that joins above-mentioned 115 ℃ was reacted in two hours, dripped and continued reaction 4h under rear 115 ℃;
3) separation of comb type polysiloxane crude oil demulsifier
After hydrosilation reaction is completed, reaction product is poured in separating funnel dissolved with the 50ml methylene dichloride, then use the NaHCO of 0.05mol/L
3Solution is regulated PH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride and unreacted methyl methacrylate with Rotary Evaporators, namely gets comb type polysiloxane crude oil demulsifier H.
Emulsion splitter for above-mentioned preparation, long celebrating Baota District crude oil is carried out breakdown of emulsion experiment (crude oil emulsion is formed by long Qing Zichang district's dewatered oil and sewage configuration), specifically with reference to oil and gas industry standard SY/T 5821-2000, the breakdown of emulsion result shows to have outstanding dehydrating effect, and dehydration rate reaches 94.5%
By embodiment as can be known, comb type polysiloxane crude oil demulsifier has the advantages such as the breakdown of emulsion ability is strong, minute water speed is fast, the breakdown of emulsion temperature is low, applied widely, is a kind of novel crude oil demulsifier.
Claims (7)
1. a comb type polysiloxane crude oil demulsifier, is characterized in that, its structural formula is as follows:
In formula: R
1Be propylene-glycol-based, octadecanol base, tetramethylolmethane base, quadrol base, alkyl phenolic resin base, polyethylene polyamine base;
R2 is methyl methacrylate base, styryl, butyl acrylate base, Isooctyl acrylate monomer base;
Wherein, n=1～50; X=1～20; Y=1～50; Z=1～30; A=20～50; B=30～60.
2. a preparation method who combs type polysiloxane crude oil demulsifier, is characterized in that, comprises the following steps:
1) in molfraction, add the containing hydrogen silicone oil of S part in reaction solvent, and to add catalyzer Platinic chloride to concentration be 60～120ppm, the reactant that then adds T part carries out hydrosilation reaction at 80～120 ℃, and the reaction times is 6～10h;
Described reactant is according to vinylformic acid polyoxyethylene polyoxypropylene ester: the mixture that the mol ratio of methacrylic acid: methacrylic ester=x:y:z is mixed the three, x=1～20, y=1～50, z=1～30; S:T=1:1～1.2;
Described vinylformic acid polyoxyethylene polyoxypropylene ester is vinylformic acid propylene glycol polyoxyethylene polyoxypropylene ester, vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester, vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester, vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester, vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester or acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester; It is prepared as:
With a kind of and vinylformic acid in propylene glycol polyoxyethylene poly-oxygen propylene aether, alkyl phenolic resin polyoxyethylene poly-oxygen propylene aether, polyethylene polyamine polyoxyethylene poly-oxygen propylene aether, ethylenediamine polyoxyethylene polyethenoxy ether, octadecanol polyoxyethylene polyoxypropylene, pentaerythritol polyoxyethylene poly-oxygen propylene aether in molar ratio 1:1.2 mix, add again the toluenesulphonic acids of quality 2～6% after mixing and 0.6～1.2% Resorcinol, react 6h～8h under 120～145 ℃; After question response is completed, reaction product is dissolved with methylene dichloride, regulate pH to neutral with NaOH solution, shake up rear standing demix, tell subnatant, remove methylene dichloride, obtain vinylformic acid polyoxyethylene polyoxypropylene ester;
2) after hydrosilation reaction is completed, reaction product with extracting dissolution with solvents, is regulated pH to neutral, shake up rear standing demix, collect the layer that comprises reaction product, remove and extract solvent, obtain comb type polysiloxane crude oil demulsifier.
3. the preparation method of comb type polysiloxane crude oil demulsifier as claimed in claim 2, is characterized in that, described reaction solvent is Virahol, and the extraction solvent is methylene dichloride.
4. the preparation method of comb type polysiloxane crude oil demulsifier as claimed in claim 2, is characterized in that, in massfraction, the hydrogen content of described containing hydrogen silicone oil is 0.1～0.25%.
5. the preparation method of comb type polysiloxane crude oil demulsifier as claimed in claim 2, is characterized in that, described acrylate is methyl methacrylate, methyl acrylate, butyl acrylate or Isooctyl acrylate monomer.
6. the preparation method of comb type polysiloxane crude oil demulsifier as claimed in claim 2, it is characterized in that, described add containing hydrogen silicone oil and Platinic chloride in reaction solvent after, be heated to 80～120 ℃, in 1～2h, reactant is dripped, then continue reaction 4～8h at 80～120 ℃.
7. the preparation method of comb type polysiloxane crude oil demulsifier as claimed in claim 2, is characterized in that, after described hydrosilation reaction is completed, reaction product dissolved with methylene dichloride, then uses NaHCO
3Solution is regulated pH to neutral, shakes up rear standing demix, tells subnatant, steams methylene dichloride, obtains comb type polysiloxane crude oil demulsifier.
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| CN102942956B (en) * | 2012-12-03 | 2014-12-24 | 菏泽科达化学化工有限公司 | Organic silicon resin grafted crude oil demulsification agent and preparation method thereof |
| CN104498080B (en) * | 2014-12-05 | 2016-03-23 | 成都华阳兴华化工有限公司 | Oil soluble condensate oil emulsion splitter and preparation method thereof |
| CN105367802A (en) * | 2015-11-20 | 2016-03-02 | 陕西科技大学 | Polyether modified phenyl hydrogen-containing silicone oil and preparation method thereof |
| CN105694044B (en) * | 2016-04-11 | 2019-10-01 | 南京大学 | A kind of polysiloxanes of carboxyl functional and preparation method thereof |
| CN106479559A (en) * | 2016-09-27 | 2017-03-08 | 中国石油天然气股份有限公司 | Crude oil demulsifier containing organic silicon and preparation method thereof |
| CN108003917A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of low temperature crude oil demulsifier |
| CN108102631A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of acrylamide copoly type demulsifier and preparation method thereof |
| CN108085053B (en) * | 2017-12-07 | 2020-04-17 | 中海油天津化工研究设计院有限公司 | Catalytic cracking slurry oil de-solidification agent and preparation method thereof |
| CN110387255A (en) * | 2018-04-23 | 2019-10-29 | 盘锦富隆化工有限公司 | A kind of non-ionic water-soluble heavy crude desalination demulsifier and preparation method thereof |
| CN109880651B (en) * | 2019-02-15 | 2021-06-11 | 广州赫尔普化工有限公司 | Polysiloxane crude oil demulsifier and preparation method thereof |
| CN110256680B (en) * | 2019-07-10 | 2021-02-26 | 重庆市畜牧科学院 | Polysiloxane block polyether for preparing decoquinate emulsion and synthesis method thereof |
| CN114195300B (en) * | 2021-12-08 | 2023-12-05 | 珠海谦信新材料有限公司 | Treatment system for waste residue liquid of acetate esterification kettle |
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| CN101328429A (en) * | 2008-07-24 | 2008-12-24 | 中国石油天然气股份有限公司 | Demulsifier for dehydrating heavy viscous oil with high sulfur content |
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