CN104774645B - The preparation method of low temperature polyether type thick oil demulsifying agent - Google Patents
The preparation method of low temperature polyether type thick oil demulsifying agent Download PDFInfo
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- CN104774645B CN104774645B CN201410010762.XA CN201410010762A CN104774645B CN 104774645 B CN104774645 B CN 104774645B CN 201410010762 A CN201410010762 A CN 201410010762A CN 104774645 B CN104774645 B CN 104774645B
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Abstract
The present invention relates to a kind of preparation method and its usage of low temperature polyether type thick oil demulsifying agent, method includes the synthesis of alkylphenol-polyethenoxy propylene ether polymer and the preparation of polyether type thick oil demulsifying agent.The thick oil demulsifier is reacted using alkyl phenol polymer with polyoxyethylenepropylene ether, using solid super-strong acid as catalyst, triggers alkylphenol polymerization to obtain polyether high molecular compound.Then addition conditioning agent and solvent obtain polyether-type high-efficient demulsifier.Experiment shows that this demulsifier is high to the fast dehydration rate of rate of water loss of viscous crude, and using effect is good under low temperature, a large amount of heating energy sources are saved, and usage amount is relatively fewer, crude oil demulsification dehydration cost is reduced, there is important practical significance to crude oil and refinery's breaking emulsion and dewatering.
Description
Technical field
The invention provides a kind of preparation method of demulsifier, specifically belong to the preparation of low temperature polyether type thick oil demulsifying agent
Method and application thereof.
Background technology
In recent years, the increase with oilfield exploitation amount and the purposes of various oil recovery techniques, Produced Liquid comprehensive water cut is increasingly
Height, Produced Liquid situation is become increasingly complex, and intractability is continued to increase, and oil field old Produced Liquid comprehensive water cut has reached 95%
More than；And viscous crude contains the natural interface active agent such as higher colloid, asphalitine, causes emulsion of crude oil viscosity big, flowing
Property poor, oil-water interfaces film-strength increase, water droplet is difficult aggregation, and breaking emulsion and dewatering is difficult.
Current domestic each oil field generally uses heat chemistry or electrochemistry breaking emulsion and dewatering technology, and it is big that existing process has power consumption
After (dehydration temperaturre is high, reaches 90 DEG C), complex manufacturing, dehydration the problems such as water quality inferiority, pollution environment, it is impossible to meet viscous crude and break
The need for breast dehydration, in the urgent need to research and development efficiently, low consumption, pollution-free or low stain demulsifier and high-end simple
Technological process.
Chemical demulsification method is the wider a kind of breaking method of purposes in recent years, is to change emulsion liquid by adding demulsifier
The interfacial property of system, is allowed to be changed into unstable from relatively stablizing, so as to reach the purpose of demulsification.It is generally believed that the demulsification of demulsifier
Performance depends primarily on the hydrophilic/lipophilic ability of demulsifier and the ability of destruction interfacial film.It is species about crude oil demulsifier, broken
The selection of emulsion, performance evaluation, Mechanismic, the relation research of emulsification structure and demulsification performance have had substantial amounts of document report
Road.In recent years, the research of chemical demulsification is concentrated mainly on the demulsifier of design and synthesis different structure, such as polyether-type, polyamide
The evaluation of type and polyacrylie-type demulsifier and its demulsification performance.In addition, different types of demulsifier is compounded to obtain
High performance demulsifying agent is also one of main direction of studying in recent years.The chemical demulsifier studied both at home and abroad at present is main broken in tradition
It is modified on the basis of emulsion, main method, which has, to be changed head, changes tail, first bone, chain extension, grafting, crosslinking and compounding etc., and most is broken
Emulsion there are problems that production cost is high, raw materials for production are inflammable and explosive and, especially raw material oxirane chemical property is lived
Sprinkle, with carcinogenesis.
The content of the invention
The purpose of the present invention is that demulsifier consumption is big, dehydration temperaturre is high, rate of water loss is slow, wide when overcoming current viscous crude processing
The shortcomings of spectrality is poor, and a kind of preparation method and its usage of low temperature polyether type thick oil demulsifying agent is provided.
The technical problem solved required for invention, can be achieved through the following technical solutions：
It is used as the first aspect of the present invention, a kind of preparation method of low temperature polyether type thick oil demulsifying agent, it is characterised in that bag
Include following steps：
(1) alkyl phenol dimer is synthesized：By paraformaldehyde, absolute ethyl alcohol, alkyl phenol in molar ratio 10 at 50~70 DEG C:
1:1 adds three-necked flask, adds 3~5h of molecular sieve catalyst back flow reaction and is cooled to room temperature, decompression steams solvent and obtains alkyl
Phenol dimer；
(2) alkyl phenol polymer is synthesized：Quality hundred is calculated by the intermediate dimer of above-mentioned (1) synthesis and with the dimer
Divide than being added for 1~3% solid KOH in reactor, vacuumize and be passed through after N2 displacements, addition paraformaldehyde wherein poly first
Aldehyde is 5 with alkyl phenol group molar ratio:1~2, lower 125 DEG C of the heating of stirring keeps pressure to be 1Mpa, after the reaction 2.5h times again
5~6h of product reflux made from adding (1), is cooled to room temperature, and decompression steams solvent, produces alkyl phenol polymer；
(3) synthesis of alkylphenol-polyethenoxy propylene ether polymer：Polyoxyethylenepropylene ether and product made from (2) are pressed
Mol ratio 2:0.5~1 ratio stirring, while adding petroleum ether is heated to 60~80 DEG C of insulation 1h, in terms of alkyl phenol polymer,
It is incorporated as the solid super-strong acid SO of 2~3% mass percents4 2-/Al2O3, continue to react 3h, be warming up to 90~100 DEG C and steam stone
Oily ether, filtering removes solid super-strong acid, and alkylphenol-polyethenoxy propylene ether polymer can be obtained through separation；
(4) prepared by efficient cryogenic polyethers thick oil demulsifier：By the polymer and conditioning agent, diluent obtained by step (3)
By mass percentage, with 2:1:2 mode carries out well mixed i.e. obtained corresponding function demulsifier.
Wherein, the mol ratio of alkyl phenol and formaldehyde is 1 in the synthesis of alkyl phenol dimer：10.
Wherein, alkyl phenol polymer synthesis paraformaldehyde and alkyl phenol group molar ratio are 5:1~2.
Wherein, polyoxyethylenepropylene ether and poly alkyl phenol mol ratio are 2:0.5~1.
Wherein, alkyl phenol polymer synthesis paraformaldehyde and alkyl phenol group molar ratio are 5:1~2.
Wherein, polyoxyethylenepropylene ether and poly alkyl phenol mol ratio are 2:0.5~1.
Further comprise the steps：
(1) alkyl phenol dimer is synthesized
In the three-necked flask equipped with reflux condensing tube, add 27g paraformaldehydes according to reaction ratio and (contain formaldehyde
0.9mol), under 70ml absolute ethyl alcohols and HY molecular sieve catalysts, stirring condition, 10~20ml industrial goods nonyl phenols, heating are added
To 50~60 DEG C of back flow reaction 5h, room temperature is cooled to, solvent is removed under reduced pressure, intermediate dimer is made stand-by；
(2) synthesis of alkyl phenol polymer
Solid KOH of the mass percent as 1-3% is calculated by intermediate dimer made from the first step and using the intermediate
Added with molecular sieve catalyst in autoclave, be evacuated to 0.02MPa, be passed through nitrogen and replace repeatedly after 4 times, according to selected
The addition molal quantity m of fixed alkyphenol groups, the paraformaldehyde of 3m moles of addition, is warming up to 100~150 DEG C under agitation,
Then it is 1MPa to keep pressure, is reacted 2.5 hours, adds the product of 15g second steps, back flow reaction 6h.It is cooled to room temperature,
Remove solvent under reduced pressure.Stop reaction, be cooled to room temperature, the alkane of product, as following structural formula is taken out from autoclave
Base phenol polymer.
(3) synthesis of alkylphenol-polyethenoxy propylene ether polymer：
In 500ml flasks equipped with agitator, reflux condensing tube, thermometer and nitrogen protection device, 10~20ml is added
Alkyl phenol polymer compounds, 20ml polyoxyethylene and propylene ether, 60ml petroleum ethers, after mechanical agitation is uniform, add quality point
Number is the solid super-strong acid SO of 1~3% (in terms of alkyl phenol polyoxy ether tripolymer compound)4 2-/Al2O3, 95 DEG C are warming up to, is changed
Water knockout drum, steams petroleum ether, is continuously heating to 145 DEG C, 2.5h is reacted at this temperature, be cooled to after room temperature and be filtered to remove solid
Super acids, anhydrous sodium sulfate is added into filtrate, is removed water, is separated through silica gel column chromatography, and purification obtains light yellow viscous liquid,
Solvent is removed, faint yellow decorating film, as alkylphenol-polyethenoxy propylene ether is obtained.
R=CnH2n+ 1, n=8~16
(4) prepared by low temperature polyether type thick oil demulsifying agent：Polymer and conditioning agent, diluent obtained by step (3) is pressed
Parts by weight are calculated, with 2:1:2 mode carries out well mixed i.e. obtained corresponding function demulsifier.
It is used as the second aspect of the present invention, the use of the demulsifier of the preparation method preparation of low temperature polyether type thick oil demulsifying agent
On the way, it is characterised in that the low-temperature demulsification for viscous crude.
Beneficial effects of the present invention：
The present invention provides a kind of preparation method and its usage of low temperature polyether type thick oil demulsifying agent, overcomes current viscous crude to handle
When the shortcomings of demulsifier consumption is big, dehydration temperaturre is high, rate of water loss is slow, broad spectrum activity is poor.
Embodiment
Below in conjunction with specific embodiment, make progressive explanation to the present invention.It should be understood that following examples are merely to illustrate this hair
It is bright not for limit the scope of the present invention.
The preparation of the low temperature polyether type thick oil demulsifying agent of embodiment 1
A kind of preparation method of low temperature polyether type thick oil demulsifying agent, comprises the following steps.
1st, alkylphenol-polyethenoxy propylene ether polymer is synthesized
(1) alkyl phenol dimer is synthesized：In the 250ml three-necked flasks equipped with reflux condensing tube, according to reaction ratio plus
Enter under 27g paraformaldehydes (containing formaldehyde 0.9mol), 70ml absolute ethyl alcohols and 0.5g HY molecular sieve catalysts, stirring condition, add
115ml industrial goods nonyl phenols, are heated to 58 DEG C of back flow reaction 5h, are cooled to room temperature, remove solvent under reduced pressure, and intermediate dimerization is made
Thing is stand-by；
(2) alkyl phenol polymer is synthesized：Quality percentage is calculated by intermediate dimer obtained above and with the intermediate
Added than the solid KOH for 1% and molecular sieve catalyst in autoclave, be evacuated to 0.02MPa, be passed through nitrogen and put repeatedly
Change after 4 times, according to the addition molal quantity m of selected alkyphenol groups, the paraformaldehyde of 3m moles of addition rises under agitation
Temperature keeps pressure to be 1MPa to 125 DEG C, then, reacts 2.5 hours, adds the product of 15g second steps, back flow reaction 6h.
Room temperature is cooled to, solvent is removed under reduced pressure.Stop reaction, be cooled to room temperature, product is taken out from autoclave.
(3) synthesis of alkylphenol-polyethenoxy propylene ether polymer：Equipped with agitator, reflux condensing tube, thermometer and
In the 500ml flasks of nitrogen protection device, addition 108ml alkyl phenols polymer compounds, 20ml polyoxyethylene and propylene ether,
60ml petroleum ethers, after mechanical agitation is uniform, add the solid super-strong acid that mass fraction is 1% (in terms of alkyl phenol polymer)
SO42-/ Al2O3, is warming up to 95 DEG C, changes water knockout drum, steam petroleum ether, is continuously heating to 145 DEG C, 2.5h is reacted at this temperature,
It is cooled to after room temperature and is filtered to remove solid super-strong acid, anhydrous sodium sulfate is added into filtrate, remove water, through silica gel column chromatography point
From purification obtains light yellow viscous liquid, removes solvent, obtains faint yellow decorating film, as alkylphenol-polyethenoxy propylene ether is more
Polymers.
2nd, the preparation method of low temperature polyether type thick oil demulsifying agent
Product in above-described embodiment, 1 is added into conditioning agent and diluent, by alkylphenol-polyethenoxy propylene ether poly
Thing, aliphatic polyoxyalkylene phosphate and methanol are according to 2:1:2 modes are mixed, and produce low temperature thick oil demulsifier, are formulated as follows：
Embodiment 2 is detected
Dehydration experiment is pressed《Crude oil demulsifier performance detection method (bottle examination method)》Carry out.
Specific comparative example is as follows：
1st, the demulsification of prince wife Cao pasture crude oil
Sample size：20ml demulsifier dosages：30ppm demulsification temperature：80℃
Viscous crude property：
Water content：10.5% ρ 20:912.7kg/m3
Kinematic viscosity (50 DEG C):47.89mm2/ s freezing points：-6℃
Wax content：7.17% colloid：15.76%
Asphalitine：0.92%, 1 is shown in Table in detail.
The parameter of table 1
Note：DIS3567 and DB9393 are external product, and WDP-10 is Xi'an chemical plant product, and DP-2 is Dongying chemical industry
Factory's product, PRD-9016 provides product for producer.
2nd, the demulsification of flower crude oil is flowed
Sample size：20ml demulsifier dosages：30ppm demulsification temperature：80℃
Viscous crude property：
Water content：11.2% ρ 20:932.4kg/m3
Kinematic viscosity (50 DEG C):120.4mm2/ s freezing points：-8℃
Wax content：6.4% colloid：21.29%
Asphalitine：2.91%, 2 are shown in Table in detail.
The parameter of table 2
Note：DIS3567 and DB9393 are external product, and WDP-10 is Xi'an chemical plant product, and DP-2 is Dongying chemical industry
Factory's product, PRD-9016 provides product for producer.
As can be seen from Table 1 and Table 2, the demulsifier that prepared by the present invention is on sale broken with existing use and both at home and abroad well-known producer
Emulsion is compared, fast with low temperature dewatering speed, and dehydrating amount is big, and the advantages of abjection water is clear is especially brighter to thick oil emulsion breaking advantage
It is aobvious.
The embodiment to the present invention is illustrated above, but the present invention is not limited thereto, without departing from
Spirit of the invention, the present invention can also have various change.
Claims (3)
1. the preparation method of low temperature polyether type thick oil demulsifying agent, it is characterised in that comprise the following steps：
(1) alkyl phenol dimer is synthesized：By paraformaldehyde, absolute ethyl alcohol, alkyl phenol in molar ratio 10 at 50~70 DEG C:1:1
Three-necked flask is added, 3~5h of molecular sieve catalyst back flow reaction is added and is cooled to room temperature, decompression steams solvent and obtains alkyl phenol two
Polymers；
(2) alkyl phenol polymer is synthesized：Mass percent is calculated by the intermediate dimer of above-mentioned (1) synthesis and with the dimer
Added for 1~3% solid KOH in reactor, vacuumize and be passed through N2After displacement, add paraformaldehyde wherein paraformaldehyde with
Alkyl phenol group molar ratio is 5:1~2,125 DEG C are warming up under stirring and keeps pressure to be 1Mpa, is added again after the reaction 2.5h times
Enter 5~6h of product reflux made from (1), be cooled to room temperature, decompression steams solvent, produces alkyl phenol polymer；
(3) synthesis of alkylphenol-polyethenoxy propylene ether polymer：By polyoxyethylenepropylene ether and product made from (2) by mole
Than 2:0.5~1 ratio stirring, while adding petroleum ether is heated to 60~80 DEG C of insulation 1h, in terms of alkyl phenol polymer, is added
For the solid super-strong acid SO of 2~3% mass percents4 2-/Al2O3, continue to react 3h, be warming up to 90~100 DEG C and steam petroleum ether,
Filtering removes solid super-strong acid, and alkylphenol-polyethenoxy propylene ether polymer can be obtained through separation；
(4) prepared by efficient cryogenic polyethers thick oil demulsifier：Polymer and conditioning agent, diluent obtained by step (3) is pressed into matter
Percentage is measured, with 2:1:2 mode carries out well mixed i.e. obtained corresponding function demulsifier.
2. according to the preparation method described in claim 1, it is characterised in that：The conditioning agent is aliphatic polyoxyalkylene phosphate, diluent
For methanol.
3. the purposes of demulsifier prepared by a kind of preparation method of low temperature polyether type thick oil demulsifying agent as claimed in claim 1,
Characterized in that, the low-temperature demulsification for viscous crude.
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| CN113634191B (en) * | 2021-07-23 | 2022-09-23 | 中山市钧纬新材料科技有限公司 | Comb-type alkylphenol polyoxyethylene ether water-based dispersant and preparation method thereof |
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2014
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Patent Citations (6)
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|---|---|---|---|---|
| US4054554A (en) * | 1975-03-31 | 1977-10-18 | Petrolite Corporation | Dehazing compositions |
| JPH06126104A (en) * | 1992-07-17 | 1994-05-10 | Toho Chem Ind Co Ltd | Demulsiying agent for electric demineralization |
| JP2007100028A (en) * | 2005-10-07 | 2007-04-19 | Sumitomo Bakelite Co Ltd | Method for producing novolak-type phenol resin |
| CN102453496A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | De-emulsifier and demulsification method for hydrocarbon oil |
| CN102584641A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Process for preparing alkylphenol formaldehyde oligomer sulfonate |
| CN102618242A (en) * | 2012-02-29 | 2012-08-01 | 西安胜泰能源科技有限公司 | Oil-displacing agent as Gemini surfactant |
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