CN102432888A - 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 handled, relate to a kind of comb type ZGK 5 crude oil demulsifier and preparation method thereof.
Background technology
Crude oil demulsifier is to implement dehydrating of crude oil to handle 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 got into the later stage in succession, the continuous application of various oil field chemicals makes the crude oil demulsification more and more difficult.In addition, because different local geographical environment is different, the composition difference of crude oil is very big; Requirement to crude oil demulsifier is also inequality; Existing crude oil demulsifier breakdown of emulsion ability can not satisfy current needs, and it is strong therefore to be badly in need of a kind of breakdown of emulsion ability of exploitation, the novel crude oil emulsion splitter 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 flexibility.Application number is that 98113742.3 Chinese patent discloses a kind of crude oil demulsifier and preparation method thereof, is that initiator makes oxyethane, propylene oxide block polyethers and must adapt to the emulsion splitter of viscous crude with multi isocyanate crosslinking with terepthaloyl moietie or Ucar 35.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, TEB 3K, methyl acrylate, Bing Xisuandingzhi, Isooctyl acrylate monomer, vinylformic acid and methylacrylic acid, have good breaking emulsion and dewatering effect.Application number is the preparation that 200910113488.8 Chinese patent discloses a kind of organosilicon type crude oil demulsifier, with organic silicon polyether and tolylene diisocyanate react crude oil demulsifier, 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 ZGK 5 crude oil demulsifier and preparation method thereof, and it is few to have a consumption, divides water fast, and the breakdown of emulsion temperature is low, advantage applied widely.
The present invention realizes through following technical scheme:
A kind of comb type ZGK 5 crude oil demulsifier, its structural formula is following:
In the 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 TEB 3K base, styryl, Bing Xisuandingzhi 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 ZGK 5 crude oil demulsifier may further comprise the steps:
1) in molfraction, in reaction solvent, add the containing hydrogen silicone oil of S part, and to add the catalyzer Platinic chloride be 60～120ppm to concentration, the reactant that adds T part then 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 mol ratio of methylacrylic acid: methacrylic ester=x: y: z is with three's blended mixture, x=1～20, y=1～50, z=1～30; S: T=1: 1～1.2;
2) treat that hydrosilation reaction is accomplished after, reaction product with extracting dissolution with solvents, is regulated pH to neutral, shake up the back standing demix, collect the layer that comprises reaction product, remove the extraction solvent, obtain comb type ZGK 5 crude oil demulsifier.
Described reaction solvent is a Virahol, and the extraction solvent is a 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 Ucar 35 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 Ucar 35 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, the phenol amine aldehyde resin polyoxyethylene poly-oxygen propylene aether was mixed in 1: 1.2 in molar ratio; Add the toluenesulphonic acids of quality 2～6% after mixing and 0.6～1.2% Resorcinol again, react 6h～8h down at 120～145 ℃;
Question response dissolves reaction product after accomplishing with methylene dichloride, regulate pH value to neutral with NaOH solution, shakes up the back standing demix, tells subnatant, removes methylene dichloride, obtains vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester.
Described propenoate is TEB 3K, methyl acrylate, Bing Xisuandingzhi, Isooctyl acrylate monomer or is vinylbenzene.
Be heated to 80～120 ℃ described in reaction solvent, the adding after containing hydrogen silicone oil and the Platinic chloride, in 1～2h, reactant dripped, and continues to react 4～8h at 80～120 ℃ then.
Described hydrosilation reaction dissolves reaction product after accomplishing with methylene dichloride, use NaHCO then
3Solution is regulated pH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride, obtains comb type ZGK 5 crude oil demulsifier.
Compared with prior art, the present invention has following beneficial technical effects:
Comb type ZGK 5 crude oil demulsifier provided by the invention; It is modification to silicone oil; Pass through hydrosilation reaction; On the linear polysiloxanes of silicone oil, connect vinylformic acid polyoxyethylene polyoxypropylene ester, methylacrylic acid, propenoate respectively, and can through dehydration test three's ratio be adjusted according to the demands of different of different crude oils composition.
Further, for the requirement of different crude oils breakdown of emulsion, can adopt different types of vinylformic acid polyoxyethylene polyoxypropylene ester, propenoate and silicone oil to react.
Comb type ZGK 5 crude oil demulsifier provided by the invention; Can not only reduce oil water interfacial tension and boundary strength, and have good hydrophilic, oleophylic ability, make product be applicable to oil-in-water-type crude oil emulsion and water-in-oil-type crude oil emulsion; It is few to have consumption; Advantages such as branch water is fast, and the breakdown of emulsion temperature is low, and is applied widely.
Embodiment
Below in conjunction with concrete embodiment and result of use the present invention is done further detailed description, said is to explanation of the present invention rather than qualification.
Comb type ZGK 5 crude oil demulsifier provided by the invention; It is modification to silicone oil; Through hydrosilation reaction, on the linear polysiloxanes of silicone oil, connect vinylformic acid polyoxyethylene polyoxypropylene ester, methylacrylic acid, propenoate respectively, its structural formula is as follows:
In the 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 TEB 3K base, styryl, Bing Xisuandingzhi 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 ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester
Take by weighing Ucar 35 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 140 ℃, back flow reaction 6h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 14.12g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 110 ℃;
After claiming that prepared vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester 12.98g, methylacrylic acid 1.06g, TEB 3K 1.25g mix; Join slow dropping of above-mentioned 110 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 110 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted TEB 3K with Rotary Evaporators, promptly gets comb type ZGK 5 crude oil demulsifier A.
Embodiment 2
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester is identical with embodiment 1
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 14.12g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 110 ℃;
After claiming that prepared vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester 12.98g, methylacrylic acid 0.53g, TEB 3K 1.85g mix; Join slow dropping of above-mentioned 110 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 110 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted TEB 3K with Rotary Evaporators, promptly gets comb type ZGK 5 crude oil demulsifier B.
Embodiment 3
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester is identical with embodiment 1
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 14.12g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 110 ℃;
After claiming that prepared vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester 15.58g, methylacrylic acid 1.70g, TEB 3K 0.25g mix; Join slow dropping of above-mentioned 110 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 110 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted TEB 3K with Rotary Evaporators, promptly gets comb type ZGK 5 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 ZGK 5 crude oil demulsifier is to long celebrating Baota District crude oil different time dehydration rate
Embodiment 4
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester
Take by weighing 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 145 ℃, back flow reaction 8h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 30.00g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 115 ℃;
After claiming that prepared vinylformic acid polyethylene polyamine polyoxyethylene polyoxypropylene ester 37.66g, methylacrylic acid 1.06g, Bing Xisuandingzhi 1.58g mix; Join slow dropping of above-mentioned 115 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 115 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted Bing Xisuandingzhi with Rotary Evaporators, promptly gets comb type ZGK 5 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 ZGK 5 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 ltd all
Embodiment 5
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester
Take by weighing 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 135 ℃, back flow reaction 6h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 21.25g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 120 ℃;
After claiming that prepared acrylic acid alkyl resol polyoxyethylene polyoxypropylene ester 19.17g, methylacrylic acid 1.06g, Isooctyl acrylate monomer 2.27g mix; Join slow dropping of above-mentioned 120 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 120 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted Isooctyl acrylate monomer with Rotary Evaporators, promptly gets comb type ZGK 5 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 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 concrete outcome is as shown in table 3.
Table 3 comb type ZGK 5 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 ltd all
Embodiment 6
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester
Take by weighing 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 130 ℃, back flow reaction 6h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 110 ℃;
After claiming that prepared vinylformic acid octadecanol polyoxyethylene polyoxypropylene ester 31.50g, methylacrylic acid 1.06g, vinylbenzene 1.29g mix; Join slow dropping of above-mentioned 110 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 110 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted vinylbenzene with Rotary Evaporators, promptly gets comb type ZGK 5 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 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 91.7%
Embodiment 7
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester
Take by weighing 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 135 ℃, back flow reaction 6h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 115 ℃;
After claiming that prepared vinylformic acid pentaerythritol polyoxyethylene polyoxypropylene ester 27.80g, methylacrylic acid 1.06g, vinylbenzene 1.29g mix; Join slow dropping of above-mentioned 120 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 115 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted vinylbenzene with Rotary Evaporators, promptly gets comb type ZGK 5 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 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 92.8%
Embodiment 8
The preparation method of comb type ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester
Take by weighing 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 135 ℃, back flow reaction 6h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 120 ℃;
Claim prepared vinylformic acid ethylenediamine polyoxyethylene polyoxypropylene ester 22.87g, methylacrylic acid 1.06g, Isooctyl acrylate monomer 2.27g; After the mixing; Join slow dropping of above-mentioned 120 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 120 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted Isooctyl acrylate monomer with Rotary Evaporators, promptly gets comb type ZGK 5 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 ZGK 5 crude oil demulsifier may further comprise the steps:
1) preparation of vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester
Take by weighing 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 and be equipped with in the there-necked flask of whisking appliance, water trap, spherical condensation tube, TM; Be heated to 135 ℃, back flow reaction 6h;
After reaction is accomplished; Reactant is poured in the pear shape separatory funnel; Add methylene dichloride 50ml it is dissolved fully, regulate pH to neutral with the NaOH solution of 0.05mol/L then, shake up the back standing demix; Tell subnatant, steam methylene dichloride with Rotary Evaporators and promptly get product vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester;
2) hydrosilation reaction
Take by weighing containing hydrogen silicone oil (hydrogen content 0.185%) 20g, Virahol 27.0g, Platinic chloride 60ppm and add and be equipped with in the four-hole boiling flask of tap funnel, spherical condensation tube, TM, whisking appliance, be heated to 120 ℃;
Claim prepared vinylformic acid phenol amine aldehyde resin polyoxyethylene polyoxypropylene ester 36.43g, methylacrylic acid 1.06g, TEB 3K 1.25g; After the mixing; Join slow dropping of above-mentioned 115 ℃ containing hydrogen silicone oil system and reacted in two hours, drip back 115 ℃ and continue reaction 4h down;
3) separation of comb type ZGK 5 crude oil demulsifier
After hydrosilation reaction is accomplished, reaction product poured in the separating funnel dissolve, use the NaHCO of 0.05mol/L then with the 50ml methylene dichloride
3Solution is regulated PH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride and unreacted TEB 3K with Rotary Evaporators, promptly gets comb type ZGK 5 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%
Can know that through embodiment comb type ZGK 5 crude oil demulsifier has advantages such as the breakdown of emulsion ability is strong, branch water speed is fast, the breakdown of emulsion temperature is low, applied widely, is a kind of novel crude oil demulsifier.
Claims (9)
1. comb type ZGK 5 crude oil demulsifier is characterized in that its structural formula is following:
In the 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 TEB 3K base, styryl, Bing Xisuandingzhi 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 ZGK 5 crude oil demulsifier is characterized in that, may further comprise the steps:
1) in molfraction, in reaction solvent, add the containing hydrogen silicone oil of S part, and to add the catalyzer Platinic chloride be 60～120ppm to concentration, the reactant that adds T part then 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 mol ratio of methylacrylic acid: methacrylic ester=x: y: z is with three's blended mixture, x=1～20, y=1～50, z=1～30; S: T=1: 1～1.2;
2) treat that hydrosilation reaction is accomplished after, reaction product with extracting dissolution with solvents, is regulated pH to neutral, shake up the back standing demix, collect the layer that comprises reaction product, remove the extraction solvent, obtain comb type ZGK 5 crude oil demulsifier.
3. the preparation method of comb type ZGK 5 crude oil demulsifier as claimed in claim 2 is characterized in that described reaction solvent is a Virahol, and the extraction solvent is a methylene dichloride.
4. the preparation method of comb type ZGK 5 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 ZGK 5 crude oil demulsifier as claimed in claim 2; It is characterized in that described vinylformic acid polyoxyethylene polyoxypropylene ester is vinylformic acid Ucar 35 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.
6. the preparation method of comb type ZGK 5 crude oil demulsifier as claimed in claim 5 is characterized in that, being prepared as of described vinylformic acid polyoxyethylene polyoxypropylene ester:
A kind of and vinylformic acid in Ucar 35 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, the phenol amine aldehyde resin polyoxyethylene poly-oxygen propylene aether was mixed in 1: 1.2 in molar ratio; Add the toluenesulphonic acids of quality 2～6% after mixing and 0.6～1.2% Resorcinol again, react 6h～8h down at 120～145 ℃;
Question response dissolves reaction product after accomplishing with methylene dichloride, regulate pH to neutral with NaOH solution, shakes up the back standing demix, tells subnatant, removes methylene dichloride, obtains vinylformic acid Ucar 35 polyoxyethylene polyoxypropylene ester.
7. the preparation method of comb type ZGK 5 crude oil demulsifier as claimed in claim 2 is characterized in that described propenoate is TEB 3K, methyl acrylate, Bing Xisuandingzhi or Isooctyl acrylate monomer.
8. the preparation method of comb type ZGK 5 crude oil demulsifier as claimed in claim 2; It is characterized in that, described in reaction solvent, the adding after containing hydrogen silicone oil and the Platinic chloride, be heated to 80～120 ℃; In 1～2h, reactant is dripped, continue reaction 4～8h at 80～120 ℃ then.
9. the preparation method of comb type ZGK 5 crude oil demulsifier as claimed in claim 2 is characterized in that, described hydrosilation reaction dissolves reaction product after accomplishing with methylene dichloride, use NaHCO then
3Solution is regulated pH to neutral, shakes up the back standing demix, tells subnatant, steams methylene dichloride, obtains comb type ZGK 5 crude oil demulsifier.
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