CN108130122A - A kind of more quaternary amine reverse-phase emulsifiers and preparation method thereof - Google Patents

A kind of more quaternary amine reverse-phase emulsifiers and preparation method thereof Download PDF

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Publication number
CN108130122A
CN108130122A CN201711318446.9A CN201711318446A CN108130122A CN 108130122 A CN108130122 A CN 108130122A CN 201711318446 A CN201711318446 A CN 201711318446A CN 108130122 A CN108130122 A CN 108130122A
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Prior art keywords
epoxychloropropane
reverse
quaternary ammonium
ammonium salt
added dropwise
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CN201711318446.9A
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CN108130122B (en
Inventor
王惠
姚光源
潘月秋
魏淸
张迪彦
章甦
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CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)

Abstract

A kind of preparation method of multi-quaternary ammonium salt reverse-phase emulsifier of the present invention is related to the high water-content crude oil process field that the oily oil extraction in oil field in land oil field and sea generates.Preparation method of the present invention includes：Epoxychloropropane is slowly added dropwise into polyetheramine D 230 at 30 50 DEG C, control molar ratio n (D 230)/n (epoxychloropropane) is 1:2 or 1：4, after rear 4 5h of insulation reaction generations intermediate is added dropwise, 85 90 DEG C are warming up to start that the N with epoxychloropropane equimolar amounts is added dropwise, N dimethylethanolamines, 5 6h of insulation reaction, reaction product obtain faint yellow sticky shape multi-quaternary ammonium salt reverse-phase emulsifier after absolute ethyl alcohol ethyl acetate purifies and is dried in vacuo.Multi-quaternary ammonium salt reverse-phase emulsifier of the present invention has excellent breaking emulsion and dewatering effect.

Description

A kind of more quaternary amine reverse-phase emulsifiers and preparation method thereof
Technical field
The present invention relates to oil field chemical fields, and in particular to the High water cut that the oily oil extraction in oil field in land oil field and sea generates is former The preparation method of more quaternary amine reverse-phase emulsifiers in oil processing field.
Background technology
At present, majority oil field in China's comes into middle and later periods High water cut and recovers the oil the stage, gathers drive, surfactant flooding, ternary Although the use of the oil recovery techniques such as combination flooding improves crude oil produced quantity, but due to polymer, surfactant, water in Produced Liquid The interaction of insoluble particles so that Produced Liquid becomes a kind of grease system of complexity, handles these and emulsifies serious High water cut Crude oil brings new challenge to oil field production.Therefore, reverse-phase emulsifier of the exploitation with efficient demulsification performance produces reality It is significant.Reverse-phase emulsifier is divided into low molecule electrolyte, polymer, surfactant.Zhao Xi is past, Xu Junying is (hyper-branched The preparation of crude oil demulsifier and demulsification performance research [J] petroleum refinings and chemical industry, 2017,48 (4):19-23) described in paper Surfactant is divided into anionic, non-ionic, cationic, and nearly all reverse-phase emulsifier is derived by amine or amine Object prepares gained.Since multi-quaternary ammonium salt class reverse-phase emulsifier has the advantages that good water-soluble, diffusion rate is fast, become The hot spot of research.(Nguyen D, Sadeghi N, the Houston C.Chemical interactions and such as Nguyen D demulsifier characteristics for enhanced oil recovery applications[J].Energy& Fuels, 2012,26 (5):In research 2742-2750), after adding in quaternary ammonium salt, particle videomicroscopy and Focused Beam Reflectance Rate measures probe and shows that oil droplet size significantly increases, quantity is reduced, and the anionic charge on this and crude oil surface is gradually neutralized, oil The theory that coalescence occurs for drop is consistent.
The preparation process of the common multi-quaternary ammonium salt reverse-phase emulsifier of existing market is complicated, and demulsification is not good enough, and broad spectrum activity is low, To the exploitation of viscous crude oil-sand, polymer produced liquid, breaking emulsion and dewatering effect is low, is badly in need of preparing a kind of simple for process, demulsification range wide spectrum, The efficient reverse-phase emulsifier of effect.
Invention content
The technical problems to be solved by the invention are to overcome the deficiencies of the prior art and provide a kind of more quaternary amine rp demulsifications The preparation method of agent, this method preparation process is simple, reverse-phase emulsifier demulsification obtained is good, demulsification range wide spectrum, especially There is good breaking emulsion and dewatering effect for the exploitation of viscous crude oil-sand, polymer produced liquid.
The present invention is achieved especially by following technical scheme：
A kind of preparation method of more quaternary amine reverse-phase emulsifiers, including：：At 30-50 DEG C into polyetheramine D-230 slowly Epoxychloropropane is added dropwise, control molar ratio n (D-230)/n (epoxychloropropane) is 1:2 or 1：4, it is kept the temperature after being added dropwise anti- After answering 4-5h generation intermediates, it is warming up to 85-90 DEG C and starts that the N with epoxychloropropane equimolar amounts, N- dimethyl ethanols is added dropwise Amine, insulation reaction 5-6h, it is more that reaction product obtains faint yellow sticky shape after absolute ethyl alcohol-ethyl acetate purifies and is dried in vacuo Quaternary ammonium salt reverse-phase emulsifier.
Compared with existing preparation method, advantage is the preparation method of the more quaternary amine reverse-phase emulsifiers of the present invention：It closes Into simple for process, green pollution-free, for viscous crude field Produced Liquid, there is good breaking emulsion and dewatering effect.
Description of the drawings
Fig. 1 is the reaction equation of the preparation method of the more quaternary amine reverse-phase emulsifiers of the present invention.
Fig. 2 is the infrared spectrogram for preparing more quaternary amine reverse-phase emulsifier raw material polyetheramine D-230；
Fig. 3 is the infrared spectrogram of more quaternary amine reverse-phase emulsifier Y-564 made from embodiment 2.
Specific embodiment
Embodiment 1：
By 69g polyetheramines D-230 be added to equipped with thermometer, reflux condensing tube, blender four-hole boiling flask in, in 40- 55.5g epoxychloropropane is slowly added dropwise at 50 DEG C, n (D-230)/n (epoxychloropropane) is 1:2, rear insulation reaction is added dropwise 4-5h is warming up to 85-90 DEG C and starts that 53.4gN, N- dimethylethanolamines, insulation reaction 5-6h is added dropwise.Product through absolute ethyl alcohol- Ethyl acetate purifies and faint yellow sticky shape product, i.e. multi-quaternary ammonium salt reverse-phase emulsifier Y-562 is obtained after being dried in vacuo.By polyethers The reaction equation that amine D-230 prepares multi-quaternary ammonium salt reverse-phase emulsifier is shown in Fig. 1.
Embodiment 2
By 23g polyetheramines D-230 be added to equipped with thermometer, reflux condensing tube, blender four-hole boiling flask in, in 40- 74g epoxychloropropane is slowly added dropwise at 50 DEG C, n (D-230)/n (epoxychloropropane) is 1:4, rear insulation reaction 4- is added dropwise 5h is warming up to 85-90 DEG C and starts that 71.2gN, N- dimethylethanolamines, insulation reaction 5-6h is added dropwise.Product is through absolute ethyl alcohol-second Acetoacetic ester purifies and faint yellow sticky shape product, i.e. multi-quaternary ammonium salt reverse-phase emulsifier Y-564 is obtained after being dried in vacuo.
The infrared spectrogram of polyetheramine D-230 and Y-564 are shown in Fig. 2 and Fig. 3.In Fig. 2：In 3362cm-1And 3289cm-1Place Peak type for the shape of a saddle, be the symmetrical and asymmetric stretching vibration peak of N-H in primary amine；1590cm-1Locate the in-plane bending for N-H Vibration peak；1109cm-1Locate the stretching vibration peak for C-O-C.In Fig. 3：3384cm-1Locate the stretching vibration absorption for O-H keys Peak；2969cm-1And 2876cm-1For CH3- stretching vibration peak；2934cm-1For CH2- stretching vibration peak；1642cm-1For The stretching vibration peak of C-N；1478cm-1For CH2- flexural vibrations peak；1089cm-1Stretching vibration peak for C-O-C； 968cm-1Characteristic absorption peak for C-N in quaternary ammonium salt.From the comparison of Fig. 2 and Fig. 3 as can be seen that the infrared spectrum of Y-564 products The characteristic peak of primary amine disappears in figure, the characteristic peak of quaternary ammonium salt occurs, it can be determined that the product is target product multi-quaternary ammonium salt Reverse-phase emulsifier.
Performance test
More quaternary amine reverse-phase emulsifiers are compared with live medicament dehydrating effect
More quaternary amine reverse-phase emulsifier Y-562, Y-564 are compared, Y- with scene with demulsifier (referred to as live agent) 562nd, the additive amount of Y-564 is 15mg/L, and live agent additive amount is 15mg/L and 40mg/L, and breaking emulsion and dewatering effect is shown in Table 1.From table 1 can be seen that：During identical plus dosage, oil content or upper strata Water in oil amount, the breaking emulsion and dewatering of Y-564 either in lower water Effect is superior to the breaking emulsion and dewatering effect of Y-562, and the water that Y-564 is deviate from is clear；The breaking emulsion and dewatering effect of Y-564 is also superior to existing The breaking emulsion and dewatering effect of field agent, when improving when adding dosage to 40mg/L of live agent, dehydrating effect, which remains unchanged, is inferior to the de- of Y-564 Water effect.Illustrate that Y-564 has preferable demulsification to the platform crude oil.
Table 1Y-562, Y-564 and scene demulsifier breaking emulsion and dewatering Contrast on effect
It is compared with different type reverse-phase emulsifier
Y-564 and industrial routine reverse-phase emulsifier F-101 (polyether-type), BK-23 (polyacrylamide) are demulsified Dehydrating effect compares, and set temperature is 70 DEG C, and demulsifier additive amount is 15mg/L, and sedimentation time 20min the results are shown in Table 2.From For table 2 as can be seen that in 3 kinds of demulsifiers, oil content and Water in oil amount are minimum in the water of Y-564, illustrate at identical conditions The breaking emulsion and dewatering effect of multiple quaternary ammonium reverse-phase emulsifier is better than polyether-type, polyacrylamide reverse-phase emulsifier.
2 all kinds of reverse-phase emulsifier dehydrating effects of table compare

Claims (2)

1. a kind of preparation method of multi-quaternary ammonium salt reverse-phase emulsifier, which is characterized in that including：To polyetheramine D- at 30-50 DEG C Epoxychloropropane is slowly added dropwise in 230, control molar ratio n (D-230)/n (epoxychloropropane) is 1:2 or 1：4, it is added dropwise After insulation reaction 4-5h generates intermediate afterwards, it is warming up to 85-90 DEG C and starts that the N, N- bis- with epoxychloropropane equimolar amounts is added dropwise Methylethanolamine, insulation reaction 5-6h, reaction product obtain faint yellow after absolute ethyl alcohol-ethyl acetate purifies and is dried in vacuo Sticky shape multi-quaternary ammonium salt reverse-phase emulsifier.
2. the preparation method of the multi-quaternary ammonium salt reverse-phase emulsifier according to claims 1, it is characterized in that, the polyetheramine with The molar ratio of epoxychloropropane is 1：4.
CN201711318446.9A 2017-12-12 2017-12-12 Multi-quaternary ammonium salt reverse demulsifier and preparation method thereof Active CN108130122B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669261A (en) * 2019-11-17 2020-01-10 刘琴 Preparation method of composite calcium-zinc stabilizer for plastic pipeline
CN113429955A (en) * 2021-06-24 2021-09-24 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN114907559A (en) * 2022-05-13 2022-08-16 中海油(天津)油田化工有限公司 Polyether-based amphoteric water clarifier for oily sewage treatment and preparation method thereof
CN115124713A (en) * 2022-06-23 2022-09-30 麦加芯彩新材料科技(上海)股份有限公司 Ionic liquid demulsifier with four-branch structure and preparation method and application thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110669261A (en) * 2019-11-17 2020-01-10 刘琴 Preparation method of composite calcium-zinc stabilizer for plastic pipeline
CN113429955A (en) * 2021-06-24 2021-09-24 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN113429955B (en) * 2021-06-24 2022-03-11 中国矿业大学 Preparation of load type polyether polyquaternary ammonium salt reverse demulsifier and application of load type polyether polyquaternary ammonium salt reverse demulsifier in ternary combination flooding produced water treatment
CN114907559A (en) * 2022-05-13 2022-08-16 中海油(天津)油田化工有限公司 Polyether-based amphoteric water clarifier for oily sewage treatment and preparation method thereof
CN114907559B (en) * 2022-05-13 2023-09-08 中海油(天津)油田化工有限公司 Polyether-based amphoteric water scavenger for treating oily sewage and preparation method thereof
CN115124713A (en) * 2022-06-23 2022-09-30 麦加芯彩新材料科技(上海)股份有限公司 Ionic liquid demulsifier with four-branch structure and preparation method and application thereof
CN115124713B (en) * 2022-06-23 2024-01-23 麦加芯彩新材料科技(上海)股份有限公司 Ionic liquid demulsifier with four-branch structure and preparation method and application thereof

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