CN104140846B - A kind of crude oil demulsifier and preparation method thereof - Google Patents
A kind of crude oil demulsifier and preparation method thereof Download PDFInfo
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- CN104140846B CN104140846B CN201310523190.0A CN201310523190A CN104140846B CN 104140846 B CN104140846 B CN 104140846B CN 201310523190 A CN201310523190 A CN 201310523190A CN 104140846 B CN104140846 B CN 104140846B
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Abstract
The present invention relates to crude oil demulsifier and preparation method, belong to oilfield chemistry agent technical field, the compound shown in structure shown in formula I formula and solvent form；There is consumption few, the features such as interfacial activity and permeability are preferable, can fast emulsion breaking dehydration, to crude oil emulsion, there is good demulsification performance, can be applicable to crude oil conventional exploitation dehydration field.
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
More or less contain certain moisture from the crude oil of underground extraction, and form crude oil emulsion.Wet crude can not be straight
Connect refining processing, therefore need to carry out breaking emulsion and dewatering to crude oil in crude oil transmission processing procedure.The use of crude oil demulsifier is
Common crude oil demulsification dehydration method.Because crude oil demulsifier generally has very strong surface activity, preferable amphipathic property
Can, thus adding the breakdown of emulsion agent molecule in crude oil emulsion can spread to oil-water interfaces quickly, displacement or aliquot replacement go out
The emulsifying agent of absorption on oil-water interfaces, destroys the emulsifying agent film of emulsion interfaces, so that being scattered in the water droplets coalescence in crude oil
Sedimentation and and crude separation, reach the purpose of breaking emulsion and dewatering.Crude oil demulsifier common at present is polyoxyethylene ether and polyoxy third
The block copolymer of alkene ether or random copolymer.
Existing polyether type demulsifying agent can be divided mainly into following a few class：Polyethylene polyamine is initiator, is initial with phenols
Agent, with straight chain alcohols as initiator and super high molecular weight polyether-type etc..Existing demulsifier has that consumption is big, breakdown of emulsion efficiency is low
Unsharp defect with oil-water interfaces after breakdown of emulsion.
Content of the invention
The invention aims to overcome that the consumption that above-mentioned prior art exists is big, breakdown of emulsion efficiency is low and breakdown of emulsion after profit
The defect such as interface is unintelligible, provides that a kind of consumption is little, oil-water interfaces clearly crude oil demulsification after breakdown of emulsion efficiency high and breakdown of emulsion
Agent.
It is a further object to provide the preparation method of above-mentioned crude oil demulsifier.
The demulsifier of the present invention is that the compound shown in structure shown in formula I formula and solvent form；
Compound shown in described structure shown in formula I formula can utilize the raw material of commercialization by simple chemical reaction system
?.
In described structure shown in formula I formula, R is the alkoxy or halogen atom with 25 hydroxyls；X=1 20, y=1 100, n
=1‐50；Described crude oil demulsifier preferred structure is：In described formula I, the alkoxyl that R is 3 or 4 for hydroxyl value；X=8 15, y=
5 10, n=5 20；
Compound shown in described structure shown in formula I formula has spectroscopy feature as shown in Figure 1：
Wherein, in hydrogen resonant nucleus magnetic spectrum Fig. 1：Chemical shift is in described formula I for 4.2ppm and 3.6ppm positionTwo hydrogen-likes in structure, chemical shift is institute for 2.3ppm, 1.6ppm and 1.3ppm position
State in formula IThree hydrogen-likes in structure, chemical shift is 7.3ppm position
Putting is deuterochloroform solvent peak；
In infrared analysiss spectrogram 2：The vibration absorption peak being OH in described formula I at the peak of 3500 beam location, 2800
The peak of beam location is CH and CH in described formula I2Stretching vibration peak, the peak of 1750 beam location be described formula I in C
The vibration absorption peak of=O structure, the peak in 400 1500 wave-number ranges is in described formula IKnot
The skeletal vibration peak of structure；
The method preparing above-mentioned crude oil demulsifier that the present invention provides, is by the compound shown in described structure shown in formula I formula
Mix with solvent, obtain described crude oil demulsifier；The quality of compound shown in described structure shown in formula I formula and the ratio of solvent quality
It is worth for 1-30：99-70, preferred ratio is 5-10：95-90；Solvent described in described solvent is in ethyl acetate, methyl acetate
At least one.
In addition, the compound shown in structure shown in formula I formula is polyester-type macromolecule, by alkyl diacid chloride directly and Polyethylene Glycol
React or first occur polyreaction to be obtained with after many alcohol compounds react on a small quantity with Polyethylene Glycol；This compound can be according to as follows
Prepared by method：It is proportionally added into alkyl diacid chloride shown in formula II and reaction dissolvent in a kettle., pH value is adjusted to 9-11, temperature
For 0～5 DEG C.Under agitation, a small amount of formula IV and the formula compound of alkanol molecule more than V is added to carry out alkyl diacid chloride end group
Modify（Or it is not added with, direct next step）, pressure one atmospheric pressure of holding, at 0～5 DEG C, pH value is controlled to 9-11 to temperature control,
Reaction 15 minutes.Subsequently, under the conditions of high-speed stirred, the Polyethylene Glycol shown in a certain proportion of formula III is added to carry out polycondensation anti-
Should, pressure keeps an atmospheric pressure, and at 0～5 DEG C, pH value is controlled to 9-11 to temperature control, reacts 1 hour.After reaction terminates, subtract
Pressure distills out reaction dissolvent, takes out product.The y in x and formula III in formula II is with described in formula I.
The crude oil demulsifier that the present invention provides, it is few to have a consumption, the features such as interfacial activity and permeability are preferable, can be quick
Breaking emulsion and dewatering, has good demulsification performance to crude oil emulsion, can be applicable to crude oil conventional exploitation dehydration field.
Brief description
Fig. 1 is the hydrogen resonance spectrogram of compound described in formula I general structure of the present invention；
Fig. 2 is the infrared analysiss spectrogram of compound described in formula I general structure of the present invention.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Described number in example below is mass fraction.
Experimental technique used in example below if no special instructions, is conventional method.
Material used in example below, reagent etc., if no special instructions, all commercially.
Described structure shown in formula I polyester-type macromolecular compound preparation example 1：Directly reacted with Polyethylene Glycol by alkyl diacid chloride or
First and many alcohol compounds occur polyreaction to be obtained with Polyethylene Glycol after reacting, and comprise the following steps：
（1）Add alkyl diacid chloride and reaction dissolvent shown in formula II in a kettle., pH value is adjusted to 9-11, temperature is 0
～5 DEG C, under agitation, react 15 minutes；
The span of the x in formula II is：x=8‐15.
（2）Under the conditions of high-speed stirred, the Polyethylene Glycol shown in the formula III of addition carries out polycondensation reaction, and pressure keeps one
Atmospheric pressure, at 0～5 DEG C, pH value is controlled to 9-11 to temperature control, reacts 1 hour；
The span of the y in formula III is：y=5‐10；
Polyethylene Glycol shown in III with the mol ratio of alkyl diacid chloride shown in II is：1：1
（3）Vacuum distillation goes out reaction dissolvent, takes out product.
Above-mentioned steps（1）After the completion of reaction, add the compound of formula IV or structure shown in formula V in a kettle., carry out alkane
Base diacid chloride end group modification.
Embodiment 1
Compound shown in 20 grams of formula VI structural formulas is mixed with 380 grams of ethyl acetate, prepared demulsifier A.
Embodiment 2
Compound shown in 20 grams of formula VII structural formulas is mixed with 380 grams of ethyl acetate, prepared demulsifier B.
Embodiment 3
Compound shown in 20 grams of formula VIII structural formulas is mixed with 380 grams of ethyl acetate, prepared demulsifier C.
The preparation method of embodiment 46 embodiment is identical with embodiment 13
Comparative example 1：Bottle examination method breakdown of emulsion is carried out under identical same demulsifier consumption to the crude oil of Zhongyuan Oil Field oil recovery two factories, right
More as shown in table 1 than experimental result.
Recover the oil the demulsifier with formula VI general structure that two factories provide for Zhongyuan Oil Field（I.e. JS PR）.
PO is the methyl ethoxy unit after the expoxy propane open loop shown in formula VII structural formula, and EO is shown in formula VIII structure
Ethoxy unit after oxirane open loop.
This bottle examination method breakdown of emulsion is with reference to People's Republic of China's oil and gas industry standard SY/T5281 2000《Crude oil breaks
Emulsion serviceability detection method（Bottle examination method）》.
The abjection water yield of range estimation record different time, when terminating sedimentation, observed and recorded sewage color and oil-water interfaces situation.
The dehydration experiment result to Zhongyuan Oil Field oil recovery two factory's crude oil emulsions for table 1 demulsifier
Dehydration experiment result shows, the demulsifier that the present invention provides has good demulsification performance to crude oil emulsion.With
Existing JS PR demulsifier is compared, and the breakdown of emulsion time is short, and thoroughly, after dehydration, water quality is transparent, and oil-water interfaces are clear for dehydration.Can apply
In the conventional oil recovery dehydration field to crude oil emulsion.
Claims (6)
1. a kind of crude oil demulsifier is it is characterised in that the polyester-type macromolecular compound shown in structure shown in formula I formula and solvent group
Become, at least one in ethyl acetate, methyl acetate for the described solvent,
In described structure shown in formula I formula, R is the alkoxy or halogen atom with 25 hydroxyls；X=1 20, y=1 100, n=
1‐50.
2. crude oil demulsifier according to claim 1 it is characterised in that：In described formula I, the alkane that R is 3 or 4 for hydroxyl value
Epoxide；X=8 15, y=5 10, n=5 20.
3. crude oil demulsifier according to claim 1 and 2 it is characterised in that：The quality of described structure shown in formula I general formula compound
Ratio with solvent quality is 1 30：99‐70.
4. a kind of preparation method of the crude oil demulsifier described in claim 1 is it is characterised in that tie formula I described in claim 1
Compound shown in structure formula and solvent mix, and obtain described crude oil demulsifier；
The ratio of the quality of compound shown in described structure shown in formula I formula and solvent quality is 5 10：95‐90；
At least one in ethyl acetate, methyl acetate for the described solvent.
5. the preparation method of crude oil demulsifier according to claim 4 is it is characterised in that described structure shown in formula I compound is
Polyester-type macromolecule, directly reacted with Polyethylene Glycol by alkyl diacid chloride or elder generation with after many alcohol compounds react on a small quantity with poly- second
Glycol occurs polyreaction to be obtained, and comprises the following steps：
(1) add alkyl diacid chloride and reaction dissolvent shown in formula II in a kettle., pH value is adjusted to 9-11, and temperature is 0～5
DEG C, under agitation, react 15 minutes；
The span of the x in formula II is：X=8 15；
(2) under the conditions of high-speed stirred, the Polyethylene Glycol shown in the formula III of addition carries out polycondensation reaction, and pressure keeps an air
Pressure, at 0～5 DEG C, pH value is controlled to 9-11 to temperature control, reacts 1 hour；
The span of the y in formula III is：Y=5 10；
Polyethylene Glycol shown in formula III with the mol ratio of alkyl diacid chloride shown in II is：1：1；
(3) vacuum distillation goes out reaction dissolvent, takes out product.
6. the preparation method of crude oil demulsifier according to claim 5 is it is characterised in that described step (1) reaction completes
Afterwards, add the compound of formula IV or structure shown in formula V in a kettle., carry out alkyl diacid chloride end group modification,
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| MX2020004978A (en) * | 2017-11-14 | 2020-08-24 | Dow Global Technologies Llc | Method of using high molecular weight aromatic polyol diesters as demulsifiers for crude oil treatment. |
| CN108854841B (en) * | 2018-06-25 | 2020-09-29 | 长治学院 | Pyrrolidine chiral Gemini surfactant with ester group-containing connecting group and preparation method thereof |
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| US2216310A (en) * | 1938-12-12 | 1940-10-01 | Petrolite Corp | Composition of matter and method of manufacturing same |
| US5609794A (en) * | 1994-08-05 | 1997-03-11 | Exxon Chemical Patents, Inc. | Demulsifier for water-in-oil emulsions, and method of use |
| DE10329723B3 (en) * | 2003-07-02 | 2004-12-02 | Clariant Gmbh | Using alkoxylated dendritic polyesters as emulsion breakers, especially in crude oil recovery, are required in only small amounts and are biodegradable |
| BRPI0818359A2 (en) * | 2007-10-08 | 2015-04-07 | Basf Se | Use of non-dendrimeric hyperbranched polyesters and non-dendrimeric hyperbranched polyester |
| CN101402879B (en) * | 2008-11-14 | 2013-01-02 | 华东理工大学 | Multifunctional crude oil demulsifying agent and method of producing the same |
| DE102009019177A1 (en) * | 2009-04-28 | 2010-11-11 | Clariant International Ltd. | Use of biodegradable alkoxylated (meth) acrylate copolymers as crude oil emulsion breakers |
| CN102093526B (en) * | 2010-11-25 | 2012-07-25 | 句容宁武高新技术发展有限公司 | Preparation method of demulsifier for oil fields |
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