CN104140846A - Crude oil demulsifier and preparation method thereof - Google Patents
Crude oil demulsifier and preparation method thereof Download PDFInfo
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- CN104140846A CN104140846A CN201310523190.0A CN201310523190A CN104140846A CN 104140846 A CN104140846 A CN 104140846A CN 201310523190 A CN201310523190 A CN 201310523190A CN 104140846 A CN104140846 A CN 104140846A
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Abstract
Belonging to the technical field of oil field chemical agents, the invention relates to a crude oil demulsifier and a preparation method thereof. The crude oil demulsifier is composed of a compound shown as the structural general formula I and a solvent. With the characteristics of small dosage, good interfacial activity and permeability, the crude oil demulsifier can realize rapid demulsification and dehydration, has good demulsification performance on crude oil emulsions, and can be applied to the conventional extraction and dehydration field of crude oil. (formula I).
Description
Technical field
The present invention relates to a kind of crude oil demulsifier and preparation method thereof, belong to oilfield chemistry agent technical field.
Technical background
From the crude oil of underground extraction, more or less contain certain moisture, and form crude oil emulsion.Wet oil can not directly be refined processing, therefore in crude oil transmission treating processes, needs crude oil to carry out breaking emulsion and dewatering.Using crude oil demulsifier is modal crude oil demulsification dehydration method.Because crude oil demulsifier has very strong surfactivity, good hydrophilic and oleophilic performance conventionally, thereby add the emulsion splitter molecule in crude oil emulsion to oily ?water termination, to spread very soon, displacement or part are replaced the emulsifying agent adsorbing in fuel-displaced ?water termination, destroy the emulsifying agent film of emulsion interfaces, thereby make to be scattered in water droplets coalescence sedimentation in crude oil and and crude separation, reach the object of breaking emulsion and dewatering.Common crude oil demulsifier is segmented copolymer or the random copolymers of Soxylat A 25-7 and polyethenoxy ether at present.
Existing polyether type demulsifying agent mainly can be divided into following a few class: polyethylene polyamine is initiator, take phenols as initiator, take straight chain alcohols as initiator and ultra-high molecular weight polyether-type etc.Existing emulsion splitter have that consumption is large, breakdown of emulsion efficiency is low and breakdown of emulsion after the unsharp defect of water-oil interface.
Summary of the invention
The object of the invention is for overcome that the consumption that above-mentioned prior art exists is large, breakdown of emulsion efficiency is low and breakdown of emulsion after the defects such as water-oil interface are unintelligible, provide that a kind of consumption is little, breakdown of emulsion efficiency is high and breakdown of emulsion after water-oil interface crude oil demulsifier clearly.
Another object of the present invention is to provide the preparation method of above-mentioned crude oil demulsifier.
Emulsion splitter of the present invention is, by compound and the solvent composition shown in formula I general structure;
Compound shown in described formula I general structure can utilize commercial raw material to make by simple chemical reaction.
In described formula I general structure, R be with 2 ?the alkoxy or halogen atom of 5 hydroxyls; X=1 ?20, y=1 ?100, n=1 ?50; Described crude oil demulsifier preferred structure is: in described formula I, R is that hydroxyl value is 3 or 4 alkoxyl group; X=8 ?15, y=5 ?10, n=5 ?20;
Shown in described formula I general structure, compound has spectroscopy feature as shown in Figure 1:
Wherein, in hydrogen resonant nucleus magnetic spectrum Fig. 1: chemical shift is that 4.2ppm and 3.6ppm position are in described formula I
two hydrogen-likes in structure, chemical shift is that 2.3ppm, 1.6ppm and 1.3ppm position are in described formula I
structural three hydrogen-likes, chemical shift is that 7.3ppm position is deuterochloroform solvent peak;
In infrared analysis spectrogram 2: at the peak of 3500 beam location, be Zhong described formula Ⅰ ?the vibration absorption peak of OH, at the peak of 2800 beam location, be Zhong described formula Ⅰ ?CH ?He ?CH
2? stretching vibration peak, at the peak of 1750 beam location, be the vibration absorption peak of C=O structure in described formula I, 400 ?peak in 1500 wave-number ranges be in described formula I
the skeletal vibration peak of structure;
The method of the above-mentioned crude oil demulsifier of preparation provided by the invention, is that compound and solvent shown in described formula I general structure are mixed, and obtains described crude oil demulsifier; The quality of compound shown in described formula I general structure and the ratio of solvent quality are 1-30:99-70, and preferred ratio is 5-10:95-90; Described in described solvent, solvent is selected from least one in ethyl acetate, methyl acetate.
In addition, the compound shown in formula I general structure is polyester type polymer, by alkyl diacid chloride, directly reacts with polyoxyethylene glycol or first reacts with a small amount of many alcohol compounds afterwards and polyoxyethylene glycol polymerization reaction take place makes; This compound can be prepared as follows: in reactor, add in proportion alkyl diacid chloride and reaction solvent shown in formula II, pH value is adjusted to 9-11, and temperature is 0～5 ℃.Under agitation condition, add a small amount of formula IV and many alkanol molecules of formula V compound to carry out alkyl diacid chloride end group and modify (or do not add, directly next step), pressure keeps a normal atmosphere, and temperature is controlled at 0～5 ℃, and pH value is controlled as 9-11, reacts 15 minutes.Subsequently, under high-speed stirring condition, add the polyoxyethylene glycol shown in a certain proportion of formula III to carry out polycondensation, pressure keeps a normal atmosphere, and temperature is controlled at 0～5 ℃, and pH value is controlled as 9-11, reacts 1 hour.After reaction finishes, underpressure distillation goes out reaction solvent, takes out product.Described in y cotype I in x in formula II and formula III.
The features such as crude oil demulsifier provided by the invention, has consumption few, and interfacial activity and perviousness are better, can dewater by fast emulsion breaking, and crude oil emulsion is had to good demulsification performance, can be applicable to the conventional exploitation of crude oil dehydration field.
accompanying drawing explanation
Fig. 1 is the hydrogen resonance spectrogram of compound described in formula I general structure of the present invention;
Fig. 2 is the infrared analysis spectrogram of compound described in formula I general structure of the present invention.
embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Described umber in embodiment is mass fraction below.
The experimental technique using in embodiment below if no special instructions, is ordinary method.
The material using in embodiment below, reagent etc., if no special instructions, all can be from commercial channels.
Described formula I structure polyester type macromolecular compound preparation example 1: directly react with polyoxyethylene glycol or first react with many alcohol compounds afterwards and polyoxyethylene glycol polymerization reaction take place makes by alkyl diacid chloride, comprise the following steps:
(1) in reactor, add alkyl diacid chloride and reaction solvent shown in formula II, pH value is adjusted to 9-11, and temperature is 0～5 ℃, under agitation condition, reacts 15 minutes;
The span of x in formula II is: x=8 ?15.
(2) under high-speed stirring condition, the polyoxyethylene glycol shown in the formula III adding carries out polycondensation, and pressure keeps a normal atmosphere, and temperature is controlled at 0～5 ℃, and pH value is controlled as 9-11, reacts 1 hour;
The span of y in formula III is: y=5 ?10;
Shown in polyoxyethylene glycol shown in III and II, the mol ratio of alkyl diacid chloride is: 1:1
(3) underpressure distillation goes out reaction solvent, takes out product.
After above-mentioned steps (1) has been reacted, in reactor, add the compound of structure shown in formula IV or formula V, carry out alkyl diacid chloride end group and modify.
Embodiment 1
Compound shown in 20 grams of formula VI structural formulas is mixed with 380 grams of ethyl acetate, make emulsion splitter A.
Embodiment 2
Compound shown in 20 grams of formula VII structural formulas is mixed with 380 grams of ethyl acetate, make emulsion splitter B.
Embodiment 3
Compound shown in 20 grams of formula VIII structural formulas is mixed with 380 grams of ethyl acetate, make emulsion splitter C.
The preparation method of embodiment 4-6 embodiment and embodiment 1 ?3 identical
Comparative example 1: the recover the oil crude oil of two factories of Zhongyuan Oil Field is carried out to bottle examination method breakdown of emulsion under identical same emulsion splitter consumption, and contrast and experiment is as shown in table 1.
The emulsion splitter with formula VI general structure that two factories provide (be JS ?PR) recovers the oil in Zhongyuan Oil Field.
PO is the methyl ethoxy unit after the propylene oxide open loop shown in formula VII structural formula, and EO is the ethoxy unit after the oxyethane open loop shown in formula VIII structure.
This bottle examination method breakdown of emulsion with reference to the oil and gas industry standard SY/T5281 of the People's Republic of China (PRC) ?2000 < < crude oil demulsifier use properties detection methods (bottle examination method) > >.
The water yield of deviating from of different time is recorded in range estimation, while stopping sedimentation, and observed and recorded sewage color and water-oil interface situation.
Table 1 emulsion splitter is to the recover the oil dehydration experiment result of two factory's crude oil emulsions of Zhongyuan Oil Field
Dehydration experiment result shows, emulsion splitter provided by the invention has good demulsification performance to crude oil emulsion.With existing JS ?PR emulsion splitter compare, the breakdown of emulsion time is short, thoroughly, after dehydration, water quality is transparent in dehydration, water-oil interface are clear.Can be applicable to the routine oil recovery dehydration field to crude oil emulsion.
Claims (7)
1. a crude oil demulsifier, is characterized in that, by polyester type macromolecular compound and the solvent composition shown in formula I general structure,
In described formula I general structure, R be with 2 ?the alkoxy or halogen atom of 5 hydroxyls; X=1 ?20, y=1 ?100, n=1 ?50.
2. crude oil demulsifier according to claim 1, is characterized in that, in described formula I, R is that hydroxyl value is 3 or 4 alkoxyl group; X=8 ?15, y=5 ?10, n=5 ?20.
3. crude oil demulsifier according to claim 1 and 2, is characterized in that, the quality of described formula I structure general formula and the ratio of solvent quality be 1 ?30:99 ?70.
4. crude oil demulsifier according to claim 1 and 2, is characterized in that, described solvent is at least one in ethyl acetate, methyl acetate preferably.
5. a preparation method for crude oil demulsifier as claimed in claim 1, is characterized in that, compound and the solvent shown in formula I general structure described in claim 1 mixed, and obtains described crude oil demulsifier;
The quality of compound shown in described formula I general structure and the ratio of solvent quality be 5 ?10:95 ?90;
Described solvent is selected from least one in ethyl acetate, methyl acetate.
6. the preparation method of crude oil demulsifier according to claim 5, it is characterized in that, described formula I structural compounds is polyester type polymer, by alkyl diacid chloride, directly react with polyoxyethylene glycol or first react with a small amount of many alcohol compounds afterwards and polyoxyethylene glycol polymerization reaction take place makes, comprise the following steps:
(1) in reactor, add alkyl diacid chloride and reaction solvent shown in formula II, pH value is adjusted to 9-11, and temperature is 0～5 ℃, under agitation condition, reacts 15 minutes;
The span of x in formula II is: x=8 ?15;
(2) under high-speed stirring condition, the polyoxyethylene glycol shown in the formula III adding carries out polycondensation, and pressure keeps a normal atmosphere, and temperature is controlled at 0～5 ℃, and pH value is controlled as 9-11, reacts 1 hour;
The span of y in formula III is: y=5 ?10;
Shown in polyoxyethylene glycol shown in formula III and formula II, the mol ratio of alkyl diacid chloride is: 1:1;
(3) underpressure distillation goes out reaction solvent, takes out product.
7. the preparation method of crude oil demulsifier according to claim 6, is characterized in that, after step (1) has been reacted in described power 6, adds the compound of structure shown in formula IV or formula V in reactor, carries out alkyl diacid chloride end group and modifies
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| CN108854841A (en) * | 2018-06-25 | 2018-11-23 | 长治学院 | A kind of pyrrolidines chirality Gemini surface active and preparation method thereof of the linker containing ester group |
| CN111479619A (en) * | 2017-11-14 | 2020-07-31 | 陶氏环球技术有限责任公司 | Method of using high molecular weight aromatic polyol polyesters as demulsifiers for crude oil processing |
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| CN111479619A (en) * | 2017-11-14 | 2020-07-31 | 陶氏环球技术有限责任公司 | Method of using high molecular weight aromatic polyol polyesters as demulsifiers for crude oil processing |
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