CN103570862A - Demulsifying agent, and preparation method and applications thereof - Google Patents

Demulsifying agent, and preparation method and applications thereof Download PDF

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CN103570862A
CN103570862A CN201210252673.7A CN201210252673A CN103570862A CN 103570862 A CN103570862 A CN 103570862A CN 201210252673 A CN201210252673 A CN 201210252673A CN 103570862 A CN103570862 A CN 103570862A
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polyethers
accordance
unsaturated carboxylic
acid
consumption
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CN103570862B (en
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李本高
王振宇
沈明欢
李璐
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention relates to a demulsifying agent, and a preparation method and applications thereof. The preparation method comprises following steps: (1) in the presence of a interesterification catalyst and a polymerization inhibitor, a polyether and an unsaturated carboxylic acid methyl ester and/or an unsaturated carboxylic acid ethyl ester are subjected to interesterification; (2) methanol and/or ethanol is separated via reduced pressure distillation; and (3) an unsaturated carboxylic acid, water and an free polymerization initiator are added for free radical polymerization. The demulsifying agent prepared by the preparation method is suitable for demulsification and dehydration of thickened oil.

Description

A kind of emulsion splitter and its preparation method and application
Technical field
The present invention relates to a kind of emulsion splitter and its preparation method and application.
Background technology
Viscous crude is a kind of unconventional petroleum resources, and along with the minimizing day by day of conventional thin oil reserves, viscous crude resource is taken over one of energy by becoming the important strategy of China.In China, viscous crude refers to that viscosity under reservoir temperature is greater than the crude oil of 50mPa.s, according to viscosity, can be common heavy oil (50~10000mPa.s), special viscous crude (10000~50000mPa.s), super viscous crude (more than 50000mPa.s) by viscous crude Further Division.Viscous crude has that density is high, viscosity is large, bituminous matter and the high feature of gum level, if the asphalt content of Tahe Crude Oil is up to 11%.Bituminous matter and colloid are natural water-in-oil emulsifiers, can form skin shape film in water droplet surface adsorption, hinder the coalescent of water droplet, thereby the breakdown of emulsion of high bituminous matter viscous crude are puzzlement people's difficult problems always.
From the twenties in 20th century, bring into use and developed so far three generations's water-in-oil-type emulsion splitter.There is 20~thirties of 20th century first-generation emulsion splitter, it is mainly low-molecular-weight, anionic type tensio-active agent, comprising carboxylic acid type, sulfuric acid type and sulfonate type three major types, the advantage of this class emulsion splitter is low price, shortcoming be consumption large (1000mg/L), efficiency low, be subject to Influence of Electrolyte etc.; Developed 40~fifties of 20th century s-generation emulsion splitter, mainly low molecule nonionogenic tenside, as OP type, Tween type tensio-active agent, though acidproof, alkaline-resisting, the salt tolerant of this class emulsion splitter energy, but emulsion splitter consumption is large (300~500mg/L) still, and demulsification is also not ideal enough; So far developed the third generation emulsion splitter sixties in 20th century, is mainly polymer nonionic surface active agent, and as the segmented copolymer of polyoxyethylene and polyoxypropylene, its advantage is consumption few (5~100mg/L), and shortcoming is that specificity is strong.
Along with the increase of viscous oil recovery amount, its breakdown of emulsion problem is more and more outstanding, impels people constantly to find better effects if, the emulsion splitter that universality is stronger.People find in practice, and molecular weight is high, and the emulsion splitter effect of racemosus wooden fork is better.The method that improves emulsion splitter molecular weight mainly contains 3 kinds: (1) adopts new catalyst, as chainextenders (3) such as triisobutyl aluminium-methyl ethyl diketone-water or triisobutyl aluminium-methyl ethyl diketone-water-oil of mirbane system (2) use tolylene diisocyanates (TDI), on pfpe molecule, introduce the polymerisable monomers such as vinylformic acid, by polymerization, pfpe molecule amount is increased.The third method has overcome first two method catalyzer or chainextender is expensive, poisonous, product dissolves the shortcomings such as difficulty.
Patent reports more both domestic and external to polyethers, introduce the method for polymerisable monomer, as USP4,678,599 have reported and have introduced the allyl polyether of vinyl carbinol and the multipolymer of vinyl acetate or methyl methacrylate.USP5,661,220 have reported the acrylic acid polyethers of introducing and acrylic acid multipolymer.Domestic also have a similar report, as CN1137247.These inventions adopt esterification that unsaturated carboxylic acid polymer is connected with polyethers, and esterification need to be made band aqua with toluene, to separate the water of generation, make to react completely, but toluene is poisonous on the one hand, and while using toluene on the other hand, the polyether of generation can be separated out.In prior art, seldom adopt aqueous solution polymerization to prepare the method for polyether, although CN1966138 has reported a kind of preparation method of aqueous polymer polyethers, and as viscous crude reverse-phase emulsifier, but its direct polymerization and esterification in the aqueous solution, effect can not be satisfactory.
Summary of the invention
The invention provides a kind of preparation method of emulsion splitter, the emulsion splitter that adopts the present invention to prepare not only has good breaking emulsion and dewatering performance to high bituminous matter viscous crude, and has good storage stability.
A preparation method for emulsion splitter, comprising:
(1) under the existence of transesterification catalyst and stopper, the ethyl ester of the methyl esters of polyethers and unsaturated carboxylic acid and/or unsaturated carboxylic acid is carried out to transesterification reaction, described polyethers is-CH 2cH 2o-and-CH 2cH (CH 3) segmented copolymer that O-forms, it has an end group at least is hydroxyl, number-average molecular weight is 500~30000, in polyethers-CH 2cH 2o-and-CH 2cH (CH 3) mass ratio of O-is 0.1~10:1;
(2) methyl alcohol and/or ethanol are isolated in underpressure distillation;
(3) mix with unsaturated carboxylic acid, water and free crowd initiator, carry out Raolical polymerizable; The quality of polyethers raw material of step (1) of take is 1, and the consumption of unsaturated carboxylic acid is 0.01~1;
In step (1) and (3), described unsaturated carboxylic acid can be identical or different, is all selected from one or more in vinylformic acid, methacrylic acid, maleic anhydride, toxilic acid and fumaric acid.
The temperature of reaction of step (1) is 100~120 ℃, preferably 105~110 ℃.
The reaction times of step (1) is 1~24 hour, preferably 2~6 hours.
Transesterification catalyst comprises basic catalyst, an acidic catalyst, biological enzyme agent etc.In the present invention, described transesterification catalyst is preferably sulfuric acid, phosphoric acid or tosic acid.When transesterification catalyst is tosic acid, it is 0.1%~8% of polyethers raw material and esters of unsaturated carboxylic acids total mass for consumption, is preferably 0.4%~1.5%.
In step (1), described stopper is preferably Resorcinol or MEHQ, and consumption is 0.1%~1% of esters of unsaturated carboxylic acids quality, is preferably 0.2%~0.6%.
In step (1), the mass ratio of polyethers and esters of unsaturated carboxylic acids is 1~200:1, is preferably 10~130:1
The temperature of reaction of step (3) is 65~95 ℃, preferably 80~90 ℃.
The reaction times of step (3) is 1~24 hour, preferably 2~5 hours.
The quality of polyethers raw material of step (1) of take is 1, and in step (3), the consumption of unsaturated carboxylic acid is 0.025~0.15.
Described radical polymerization initiator comprises azo-compound initiator, peroxide initiator and redox initiator.In step (3), described radical polymerization initiator is preferably persulphate, hydrogen peroxide or water-soluble azo initiator.In step (3), described radical polymerization initiator is ammonium persulphate more preferably, and consumption is 2%~45% of unsaturated carboxylic acid total mass in polyethers raw material, esters of unsaturated carboxylic acids and the step (3) in step (1), is preferably 10%~20%.
The quality of the polyethers raw material in step (1) of take is 1, and in step (3), the consumption of water is 0.5~2, is preferably 0.9~1.5.
In step (1), the number-average molecular weight of described polyethers is preferably 800~25000.
In step (1), described polyethers is preferably two blocks, three blocks or Tetrablock copolymer.
In step (1), described polyethers is preferably one or more with alcohol, amine, phenol, carboxylic acid, acid amides, resol, phenol-amine resin or polyethylene polyamine initiator gained polyethers.
In step (1), the preparation method of described polyethers raw material comprises: under the existence of catalyzer and initiator, and proceed step by step anionoid polymerization, every step polymerization is used alternatingly oxyethane or propylene oxide as polymerization single polymerization monomer.Described being used alternatingly refers to that continuous two-stage polymerization is used respectively different polymerization single polymerization monomers.
In the preparation method of polyethers, preferably in two steps, three steps or four steps carry out polyreaction, every step polymerization is used alternatingly oxidative ethane or propylene oxide as polymerization single polymerization monomer.
Described initiator is preferably one or more that use in alcohol, amine, phenol, carboxylic acid, acid amides, resol, phenol-amine resin and polyethylene polyamine.
Oxyethane, the general available following catalyst system of propylene oxide carry out polymerization.The anionoid polymerization of base catalysis, this class catalyzer has Na, K, Li, KOH, NaOH, and with the most use in production is KOH and NaOH; The cationoid polymerisation of lewis acid catalysis, this class catalyzer has BF 3, AlCl 3deng; Coordinated cationic polymerization, catalyzer is metal oxygen key compound and alkaline earth metal compound etc.The present invention can adopt above-mentioned three class catalyzer, is preferably alkali catalyst, alkali metal hydroxide more preferably, and more preferably KOH and/or NaOH, its consumption is 0.1~2% of oxyethane and propylene oxide total mass.
The emulsion splitter that the present invention also provides aforesaid method to prepare.
A breaking dehydrating method for crude oil, comprising: crude oil, water filling and above-mentioned emulsion splitter mixed, and breaking emulsion and dewatering under the effect of heat and/or electric field, the quality of crude oil of take is benchmark, emulsion splitter consumption is that 20~100ppm, water injection rate are crude quality 2~50%.
Emulsion splitter of the present invention can be used for the breaking emulsion and dewatering of hydrocarbon ils, is applicable to the breaking emulsion and dewatering of viscous crude, is specially adapted to the breaking emulsion and dewatering of high bituminous matter viscous crude.Emulsion splitter of the present invention can be used in the electric desalting process of crude oil.
Embodiment
Embodiment 1
In autoclave, add 10g methyl alcohol and 1g potassium hydroxide, logical nitrogen deoxygenation, is warming up to 130 ℃, drip 100g propylene oxide, when reaction pressure no longer reduces, be cooled to 110 ℃, drip 200 grams of oxyethane, insulation, until pressure no longer reduces, obtains two block polyether D1A.
In autoclave, add 15g nonylphenolic resin (molecular weight is 1090) and 0.9g potassium hydroxide, drip 36.2g propylene oxide, when reaction pressure no longer reduces, then drip 65.8g oxyethane, control 130 ℃ of temperature of reaction, pressure 2.3kg/cm 2, treat that reacting ethylene oxide is complete, at this temperature, add 72.5g propylene oxide, obtain block polyether D1B.
In autoclave, add 5g tetraethylene pentamine, 2.4g potassium hydroxide and 400g propylene oxide, nitrogen replacement 2~3 times, is warming up to 115 ℃, keep temperature until pressure is 0, continue to react after half an hour, be warming up to 130 ℃, drip 200g oxyethane, until pressure no longer reduces, obtain block polyether D1C.
Embodiment 2
In there-necked flask, once add D1A polyethers 100g, tosic acid 0.62g, Resorcinol 0.012g, stirring is warmed up to 105 ℃, slowly drips methyl methacrylate 5.8g, dropwises, in 105 ℃ of insulation reaction 4h, methyl alcohol is removed in underpressure distillation, obtains esterification products D2A solution.
In there-necked flask, add above-mentioned D2A esterification products 29.4g, deionized water 20ml, toxilic acid 2.6g, stirs and heats up.Ammonium persulphate 4.6g is dissolved in 15ml deionized water, respectively 1.6g vinylformic acid and ammonium persulfate aqueous solution is placed in to separating funnel, treat that still liquid is warmed up to 85 ℃, starts to drip vinylformic acid and initiator.Dropwise at 85~90 ℃ of insulation reaction 3h, obtain polymerisate D3A.
Embodiment 3
In there-necked flask, once add D1B polyethers 100g, tosic acid 0.9g, Resorcinol 0.0034g, stirring is warmed up to 105 ℃, slowly drips methyl methacrylate 1.18g, dropwises, in 105 ℃ of insulation reaction 4h, methyl alcohol is removed in underpressure distillation, obtains esterification products D2B solution.
In there-necked flask, add above-mentioned D2B esterification products 14g, deionized water 10ml, methylene-succinic acid 1.44g, stirs and heats up.Ammonium persulphate 2.4g is dissolved in 9ml deionized water, respectively 0.8g vinylformic acid and ammonium persulfate aqueous solution is placed in to separating funnel, treat that still liquid is warmed up to 85 ℃, starts to drip vinylformic acid and initiator.Dropwise at 85~90 ℃ of insulation reaction 3h, obtain polymerisate D3B.
Embodiment 4
In there-necked flask, once add D1C polyethers 100g, tosic acid 0.5g, Resorcinol 0.0012g, stirring is warmed up to 105 ℃, slowly drips methyl methacrylate 0.83g, dropwises, in 105 ℃ of insulation reaction 4h, methyl alcohol is removed in underpressure distillation, obtains esterification products D2C solution.
In there-necked flask, add above-mentioned D2C esterification products 58.6g, deionized water 41ml, acrylamide 1.72g, stirs and heats up.Ammonium persulphate 9.0g is dissolved in 28ml deionized water, respectively 1.43g vinylformic acid and ammonium persulfate aqueous solution is placed in to separating funnel, treat that still liquid is warmed up to 85 ℃, starts to drip vinylformic acid and initiator.Dropwise at 85~90 ℃ of insulation reaction 3h, obtain polymerisate D3C.
Comparative example 1
In there-necked flask, once add vinylformic acid 4.2g, D1A polyethers 50g, tosic acid 0.62g, Resorcinol 0.012g, toluene 60ml, loads onto water trap, stirs and is warmed up to 125~130 ℃, and back flow reaction 8h, obtains esterification products solution.
Get above-mentioned esterification products solution, add vinylformic acid 9.3g, benzoyl peroxide 3.1g, toluene 50ml, at N 2at environment and 85 ℃, reaction 8h, steams solvent and obtains polymerisate D4.
Comparative example 2
In there-necked flask, once add vinylformic acid 0.85g, D1B polyethers 100g, tosic acid 0.9g, Resorcinol 0.0034g, toluene 173ml, loads onto water trap, and back flow reaction 8h obtains esterification products solution.
Get above-mentioned esterification products solution, add vinylformic acid 4.3g, maleic anhydride 4.3g, benzoyl peroxide 3.0g, at N 2at environment and 85 ℃, reaction 8h, steams solvent and obtains polymerisate D5.
Embodiment 5
The dehydrating effect of evaluating emulsion splitter with the outer oil transportation of Tahe, oil property is in Table 1.During experiment, by emulsion splitter (consumption is 50ppm), water filling be preheating to the stock oil of 90~100 ℃ and fully mix in mixing tank, pour in cone-shaped glass desalter, adopt DPY-2 emulsion splitter competition instrument (Jiangyan City, Jiangsu analytical instrument factory) to carry out oily water separation, electric-force gradient 2000v/cm, 80 ℃ of temperature, the water yield that time recording separates.The dehydrating effect of emulsion splitter is in Table 2.As can be seen from the table, block polyether is after acrylic acid modified, and with conventional emulsion splitter TA1031 ratio, demulsification is improved to some extent; The acrylic acid modified polyethers that emulsion splitter of the present invention is more simple, demulsification significantly improves.In addition, bad according to the package stability of the synthetic demulsifier product of comparative example, layering after placing, and emulsion splitter D3A, D3B, D3C in the embodiment of the present invention, excellent storage stability, not stratified after placing.
The outer oil transportation character of table 1 Tahe
Analyze component Analytical data
20 ℃ of density, kg/m 3 946.9
80 ℃ of viscosity, mm 2/s 203.2
10% carbon residue, % (w) 15.9
Moisture, % (w) 0.25
Total acid value, mgKOH/g 0.14
Stable hydrocarbon, % (w) 29.8
Aromatic hydrocarbons, % (w) 26.8
Colloid, %(w) 28.9
Bituminous matter, % (w) 14.5
The dehydrating effect of table 2 emulsion splitter
TA1031: take the ethylene oxide-propylene oxide block copolymer of phenol-amine resin as initiator gained
The package stability of table 3 synthetic polymer polyethers
Polyether Package stability
D4 Layering
D5 Layering
D3A Not stratified
D3B Not stratified
D3C Not stratified
Note: sintetics is at room temperature placed and within 1 month, observed stability.

Claims (27)

1. a preparation method for emulsion splitter, comprising:
(1) under the existence of transesterification catalyst and stopper, the ethyl ester of the methyl esters of polyethers and unsaturated carboxylic acid and/or unsaturated carboxylic acid is carried out to transesterification reaction, described polyethers is-CH 2cH 2o-and-CH 2cH (CH 3) segmented copolymer that O-forms, it has an end group at least is hydroxyl, number-average molecular weight is 500~30000, in polyethers-CH 2cH 2o-and-CH 2cH (CH 3) mass ratio of O-is 0.1~10:1;
(2) methyl alcohol and/or ethanol are isolated in underpressure distillation;
(3) add unsaturated carboxylic acid, water and radical polymerization initiator, carry out Raolical polymerizable; The quality of polyethers raw material of step (1) of take is 1, and the consumption of unsaturated carboxylic acid is 0.01~1;
In step (1) and (3), described unsaturated carboxylic acid can be identical or different, is all selected from one or more in vinylformic acid, methacrylic acid, maleic anhydride, toxilic acid and fumaric acid.
2. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of step (1) is 100~120 ℃.
3. in accordance with the method for claim 1, it is characterized in that, the reaction times of step (1) is 1~24 hour.
4. in accordance with the method for claim 1, it is characterized in that, in step (1), described transesterification catalyst is sulfuric acid, phosphoric acid or tosic acid.
5. in accordance with the method for claim 1, it is characterized in that, in step (1), described transesterification catalyst is tosic acid, and consumption is 0.1%~8% of polyethers raw material and esters of unsaturated carboxylic acids total mass.
6. in accordance with the method for claim 5, it is characterized in that, the consumption of described transesterification catalyst is 0.4%~1.5% of polyethers raw material and esters of unsaturated carboxylic acids total mass.
7. in accordance with the method for claim 1, it is characterized in that, in step (1), described stopper is Resorcinol or MEHQ, and consumption is 0.1%~1% of esters of unsaturated carboxylic acids quality.
8. in accordance with the method for claim 7, it is characterized in that, in step (1), the consumption of described stopper is 0.2%~0.6% of esters of unsaturated carboxylic acids quality.
9. in accordance with the method for claim 1, it is characterized in that, in step (1), the mass ratio of polyethers and esters of unsaturated carboxylic acids is 1~200:1.
10. in accordance with the method for claim 9, it is characterized in that, in step (1), the mass ratio of polyethers and esters of unsaturated carboxylic acids is 10~130:1.
11. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of step (3) is 65~95 ℃.
12. in accordance with the method for claim 1, it is characterized in that, the reaction times of step (3) is 1~24 hour.
13. in accordance with the method for claim 1, it is characterized in that, the quality of the polyethers raw material in step (1) of take is 1, and in step (3), the consumption of unsaturated carboxylic acid is 0.025~0.15.
14. in accordance with the method for claim 1, it is characterized in that, in step (3), described radical polymerization initiator is persulphate, hydrogen peroxide or water-soluble azo initiator.
15. according to the method for claim 14, it is characterized in that, in step (3), described radical polymerization initiator is ammonium persulphate, and consumption is 2%~45% of unsaturated carboxylic acid total mass in polyethers raw material, esters of unsaturated carboxylic acids and the step (3) in step (1).
16. according to the method for claim 15, it is characterized in that, the consumption of described ammonium persulphate is 10%~20% of unsaturated carboxylic acid total mass in polyethers raw material, esters of unsaturated carboxylic acids and the step (3) in step (1).
17. in accordance with the method for claim 1, it is characterized in that, the quality of polyethers raw material of step (1) of take is 1, and in step (3), the consumption of water is 0.5~2.
18. in accordance with the method for claim 17, it is characterized in that, the quality of polyethers raw material of step (1) of take is 1, and in step (3), the consumption of water is 0.9~1.5.
19. in accordance with the method for claim 1, it is characterized in that, the number-average molecular weight of described polyethers is 800~25000.
20. in accordance with the method for claim 1, it is characterized in that, described polyethers is two blocks, three blocks or Tetrablock copolymer.
21. in accordance with the method for claim 1, it is characterized in that, described polyethers is for being one or more of initiator gained polyethers with alcohol, amine, phenol, carboxylic acid, acid amides, resol, phenol-amine resin or polyethylene polyamine.
22. in accordance with the method for claim 1, it is characterized in that, in step (1), the preparation method of described polyethers raw material comprises: under the existence of catalyzer and initiator, proceed step by step anionoid polymerization, every step polymerization is used alternatingly oxyethane or propylene oxide as polymerization single polymerization monomer.
23. in accordance with the method for claim 22, it is characterized in that, in the preparation method of the polyethers described in step (1), in two steps, three steps or four steps carry out polyreaction.
24. in accordance with the method for claim 22, it is characterized in that, in the preparation method of described polyethers, described catalyzer is KOH and/or NaOH, and its consumption is 0.1~2% of oxyethane and propylene oxide total mass.
25. in accordance with the method for claim 22, it is characterized in that, in the preparation method of described polyethers, described initiator is one or more in alcohol, amine, phenol, carboxylic acid, acid amides, resol, phenol-amine resin and polyethylene polyamine.
26. emulsion splitters that obtain according to either method in claim 1~25.
The breaking dehydrating method of 27. 1 kinds of crude oil, comprise: the emulsion splitter described in crude oil, water filling and claim 28 is mixed, breaking emulsion and dewatering under the effect of heat and/or electric field, the quality of crude oil of take is benchmark, emulsion splitter consumption is that 20~100ppm, water injection rate are crude quality 2~50%.
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CN106279669A (en) * 2016-09-20 2017-01-04 洛阳市华工实业有限公司 A kind of preparation technology of coking sulfur-containing sewage demulsifier
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