CN105195034A - Water-in-oil emulsion for preparing gas hydrate, and preparation method thereof - Google Patents
Water-in-oil emulsion for preparing gas hydrate, and preparation method thereof Download PDFInfo
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- CN105195034A CN105195034A CN201510715769.6A CN201510715769A CN105195034A CN 105195034 A CN105195034 A CN 105195034A CN 201510715769 A CN201510715769 A CN 201510715769A CN 105195034 A CN105195034 A CN 105195034A
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- white oil
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- deionized water
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Abstract
The invention belongs to the technical field of emulsifiers, and concretely elates to a water-in-oil emulsion for preparing a gas hydrate, and a preparation method thereof. Raw materials for preparing the water-in-oil emulsion comprise industrial white oil, an emulsifier, a hydration promoter and deionized water, a volume ratio of the deionized water to the hydration promoter is 10:1, a volume ratio of the industrial white oil to the emulsifier is 100:4, and a volume ratio of the industrial white oil to the deionized water is 10:1-10:7. The invention also provides the preparation method of the emulsion. The water-in-oil emulsion prepared in the invention can stably exist for a long time without layering, and can be used to reduce the phase balance pressure of the hydrate and improve the generation rate of the hydrate.
Description
Technical field
The invention belongs to emulsifying agent technical field, be specifically related to water-in-oil emulsion prepared for gas hydrate and preparation method thereof.
Background technology
Emulsifying technology serves very important effect in technical fields such as oil extraction, coal industry and clean fuel oils, becomes energy-conservation and the strong behave of environmental protect pollution.Oil and water form emulsion must possess three conditions: (1) two kind of inconsistent liquid, i.e. oil and water; (2) there is a kind of emulsifying agent, to form stable emulsion; (3) make a kind of liquid dispersion in oil water mixture to the mixing energy of another kind of liquid abundance or stirring.First and the 3rd condition be not difficult to apply for present industrial level, difficult point is just suitable emulsifying agent.So, searching and functional and the emulsifying agent of economy becomes the key preparing emulsion.Being combined with gas hydrate technology of preparing by emulsifying technology is that Hydrate Technology one of developing innovates, present stage gas hydrate generation method mainly comprise Physical and chemical method.Physical comprises the modes such as tradition stirring, bubbling, spraying, carries out under certain pressure and temperature conditions.Tradition stirs the carrying out along with the time, and hydrate viscosity increases and assembles in a large number, causes stirring wasted work increase and even stirs stall, hydrate formation is interrupted.The orifice plate aperture that Bubbling method uses is little, easily blocks at hydrate formation.Equally easily there is the phenomenon of water/hydrate particle plug nozzle in spray-on process, causes hydrate formation to interrupt.Chemical method adds chemical addition agent (promoter, surfactant etc.) in reaction system, improves the correlation properties that hydrate prepares solution.To sum up, the principal element that at present prepared by restriction gas hydrate has the following aspects: the phase balance condition that (1) hydrate generates; (2) generating rate of hydrate.And these key issues are not all well solved in existing gas hydrate technology of preparing.
Summary of the invention
The object of this invention is to provide a kind of novel emulsion liquid for improving the preparation of gas hydrate.
Technical scheme of the present invention is the water-in-oil emulsion prepared for gas hydrate, its raw materials is technical white oil, emulsifying agent, hydration accelerator and deionized water, the volume ratio of deionized water and hydration accelerator is 10 ︰ 1, the volume ratio of technical white oil and emulsifying agent is 100 ︰ 4, and the volume ratio of technical white oil and deionized water is 10 ︰ 1 ~ 10 ︰ 7; Described technical white oil is industrial 3#, 5# or 7# white oil; Described emulsifying agent is SPAN-20, SPAN-60 or SPAN-80 emulsifying agent; Described hydration accelerator is pentamethylene, cyclohexane or oxolane.
Concrete, described raw materials is industrial 7# white oil, SPAN-80, pentamethylene and deionized water.
Concrete, the volume ratio of technical white oil and deionized water is 10 ︰ 3.
Present invention also offers the preparation method of described emulsion, comprise the steps:
(1) technical white oil, emulsifying agent, hydration accelerator and deionized water is prepared, the volume ratio of deionized water and hydration accelerator is 10 ︰ 1, the volume ratio of technical white oil and emulsifying agent is 100 ︰ 4, and the volume ratio of technical white oil and deionized water is 10 ︰ 1 ~ 10 ︰ 7; Described technical white oil is industrial 3#, 5# or 7# white oil; Described emulsifying agent is SPAN-20, SPAN-60 or SPAN-80 emulsifying agent; Described hydration accelerator is pentamethylene, cyclohexane or oxolane;
(2) transparent vessel put into by technical white oil and emulsifying agent; Agitator stirs 20 minutes, makes both mix; Add deionized water, then solution is stirred 20 minutes;
(3) use in first 5 days, add hydration catalyst, this solution is invert emulsion oil solution, and it becomes droplet-like to be uniformly distributed.
Concrete, in step (2), mixing speed is 200r/min.In step (1), industrial 7# white oil and deionized water volume ratio more than 10 ︰ 7, otherwise can not there will be lamination after the oil emulsion solution left standstill of configuration.
Add pentamethylene in step (2) to carry out before hydrate preparation starts, to reduce pentamethylene volatilization.The best opportunity of adding pentamethylene in practical application is before each application starts; Or 3 ~ 5 days in advance add pentamethylene and use seal of vessel, for future use.
Hydration accelerator Main Function reduces the phase balance condition that hydrate generates, and is especially good with pentamethylene effect.
In the present invention, put into clear glass beaker in step (1) or be convenient to observe transparent vessel observe oil phase proportioning situation in time.
Technical scheme of the present invention utilizes technical white oil and deionized water to form two kinds of inconsistent liquid phases, through mechanical stirring device, two kinds of liquid are fully mixed, deionized water is made to be distributed in white oil, add emulsifying agent to enable You Heshui form stable emulsification system, add the phase balance condition that pentamethylene can reduce hydrate generation.
Beneficial effect of the present invention: the mode that patent of the present invention adopts chemical method and Physical to combine, develops a kind of novel water-in-oil emulsion for reducing hydrate phase balance pressure, and promotes the generating rate of hydrate.Water-in-oil emulsion prepared by the present invention can long-time stable exist, not stratified.Water-in-oil emulsified solution prepared by the present invention is that droplet-like is uniformly distributed, and adds solution-air contact area, and compared with the aqueous solution, CH
4, CO
2greatly increase Deng solubility in emulsion.Therefore, use this emulsion effectively to facilitate the preparation of gas hydrate, improve hydrate generating rate, for hydrate purification low concentration coal-bed gas, there is very good effect, can also effectively improve CO in IGCC synthesis gas
2the rate of recovery, add simultaneously pentamethylene reduce hydrate generate phase balance condition, improve hydrate preparation condition.This emulsion can efficiently be purified low concentration coal-bed gas, and this has higher practical value to commercial Application such as the utilization of low concentration coal-bed gas and the Storage And Transportation In Solid States of natural gas.
Detailed description of the invention
Embodiment 1 emulsified oil example
(1) 100mL industry 7# white oil is added transparent beaker, the SPAN-80 of the 4mL that reinjects.Agitating device is immersed beaker and opens stirring, mixing speed is 200r/min, and mixing time is 20min;
(2), in solution 30mL deionized water slowly added, continue to stir 20min, be the water-in-oil emulsion of regulation oil-water ratio.
The drop size of laser particle analyzer (MicrotracS3500, the U.S.) to the water-in-oil emulsion of configuration is adopted to measure.When industrial 7# white oil and deionized water volume are 10:3, the average-size of emulsion droplet is 26.4 μm.Table 1 gives profit volume proportion within the scope of 10:1 ~ 10:7, the measurement result of the average-size of emulsion droplet.
Table 1 emulsion droplet average-size is measured
(3) solution prepared by step (2) is the water-in-oil emulsion of regulation oil-water ratio.Before hydrate preparation experiment, add 3mL pentamethylene again, then start relevant hydrate preparation experiment.
Embodiment 2 emulsified oil example
(1) 100mL industry 7# white oil is added transparent beaker, the SPAN-80 of the 4mL that reinjects.Agitating device is immersed beaker and opens stirring, mixing speed is 200r/min, and mixing time is 20min;
(2) 1.0mol% tetrahydrofuran solution (wherein oxolane is 3.2mL, deionized water is 70mL) is prepared, 1.0mol% tetrahydrofuran solution is slowly added the mixed solution of white oil and SPAN-80, continue to stir 20min, be the water-in-oil emulsion of regulation oil-water ratio.
The drop size of laser particle analyzer (MicrotracS3500, the U.S.) to the water-in-oil emulsion of configuration is adopted to measure.When industrial 7# white oil and deionized water volume are 10:7, the average-size of emulsion droplet is 36.98 μm.
(3) solution prepared by step (2) is the water-in-oil emulsion of regulation oil-water ratio, and the hydrate accelerant wherein adopted is oxolane, and prepared water-in-oil emulsion can be directly used in relevant hydrate preparation experiment.
The preparation of embodiment 3 hydrate
Operating procedure emulsion of the present invention being used for the experiment of hydrate separating low concentration coal bed gas is as follows, and experiment condition is 3.5MPa and 0.5 DEG C, and experimental gas is low concentration coal-bed gas (30%CH
4, 60%N
2, 10%O
2, hereinafter referred to as experiment gas 1):
Step 1: the emulsion of preparation in example 1 (is added pentamethylene.For the ratio of the industrial 7# white oil in emulsion and deionized water for 10:3) add in reactor, then reactor sealed and immerse 0.5 DEG C of water bath with thermostatic control, and coupled reaction still pipeline;
Step 2: purge reactor 3 times with experiment gas 1, get rid of the residual air in reactor;
Step 3: experimental gas 1 is passed into reactor, pressurizes reactor and is stabilized in 3.5MPa, stops air inlet;
Step 4: after reactor temperature and pressure all reach setting value, opens electromagnetic agitation and starts experiment;
Step 5: after gas pressure no longer changes in question response device, stops experiment.Adopt gas chromatograph to carry out component analysis to reacting gas and decomposition of hydrate gas, terminate experiment.Experimentally data calculate CH
4the rate of recovery and gas consumption
The low concentration coal-bed gas separating experiment step of TBAB (TBAB) system being used for contrasting is as follows:
Step 1: the TBAB solution of preparation finite concentration ratio (experiment adopts 0.29mol%, 0.6mol%, 1.0mol% tri-kinds of concentration), adds in reactor, then sealed by reactor and immerse 0.5 DEG C of water bath with thermostatic control, and coupled reaction still pipeline;
Step 2: purge reactor 3 times with experiment gas 1, get rid of the residual air in reactor;
Step 3: experimental gas 1 is passed into reactor, pressurizes reactor and is stabilized in 3.5MPa, stops air inlet;
Step 4: after reactor temperature and pressure all reach setting value, opens electromagnetic agitation and starts experiment;
Step 5: after gas pressure no longer changes in question response device, stops experiment.Adopt gas chromatograph to carry out component analysis to reacting gas and decomposition of hydrate gas, terminate experiment.Experimentally data calculate CH
4the rate of recovery and gas consumption.
Emulsion of the present invention is used for hydrate purification low concentration coal-bed gas (30%CH
4, 60%N
2, 10%O
2) experiment (operating procedure is tested identical with separating low concentration coal bed gas).Under 3.5MPa and 0.5 DEG C condition, when the industrial 7# white oil in emulsion and deionized water volume ratio are 10 ︰ 3, CH
4the gas consumption of the rate of recovery and unit mole of water is respectively 43% and 0.033mol, all stirs the CH of system higher than TBAB (TBAB) solution
4the gas consumption (0.007mol) of the rate of recovery 26% and unit mole of water.
Emulsion of the present invention is used for IGCC synthesis gas (40%CO
2, 60%H
2) in CO
2separating experiment (operating procedure is tested identical with separating low concentration coal bed gas).Under 3.0MPa and 1 DEG C condition, industrial 7# white oil in emulsion and deionized water volume ratio 10:2, the gas consumption of unit mole of water is 0.0395mol, stirs the gas consumption (0.020mol) of system unit mole of water higher than TBAB (TBAB) solution.
Experimental result shows, emulsion of the present invention gas hydrate preparation and gas separaion (low concentration coal-bed gas purify, IGCC synthesis in CO
2being separated) aspect has significant effect, and the hydrate that emulsion of the present invention can be used for other mists is equally separated (CO
2/ N
2, CH
4/ H
2, C
2h
6/ H
2deng).
Claims (5)
1. for water-in-oil emulsion prepared by gas hydrate, it is characterized in that: its raw materials is technical white oil, emulsifying agent, hydration accelerator and deionized water, the volume ratio of deionized water and hydration accelerator is 10 ︰ 1, the volume ratio of technical white oil and emulsifying agent is 100 ︰ 4, and the volume ratio of technical white oil and deionized water is 10 ︰ 1 ~ 10 ︰ 7; Described technical white oil is industrial 3#, 5# or 7# white oil; Described emulsifying agent is SPAN-20, SPAN-60 or SPAN-80 emulsifying agent; Described hydration accelerator is pentamethylene, cyclohexane or oxolane.
2. water-in-oil emulsion as claimed in claim 1, is characterized in that: described raw materials is industrial 7# white oil, SPAN-80, pentamethylene and deionized water.
3. water-in-oil emulsion as claimed in claim 1 or 2, is characterized in that: the volume ratio of technical white oil and deionized water is 10 ︰ 3.
4. the preparation method of emulsion described in any one of claims 1 to 3, is characterized in that: comprise the steps:
(1) technical white oil, emulsifying agent, hydration accelerator and deionized water is prepared, the volume ratio of deionized water and hydration accelerator is 10 ︰ 1, the volume ratio of technical white oil and emulsifying agent is 100 ︰ 4, and the volume ratio of technical white oil and deionized water is 10 ︰ 1 ~ 10 ︰ 7; Described technical white oil is industrial 3#, 5# or 7# white oil; Described emulsifying agent is SPAN-20, SPAN-60 or SPAN-80 emulsifying agent; Described hydration accelerator is pentamethylene, cyclohexane or oxolane;
(2) transparent vessel put into by technical white oil and emulsifying agent; Agitator stirs 20 minutes, makes both mix; Add deionized water, then solution is stirred 20 minutes;
(3) use in first 5 days, add hydration catalyst, this solution is invert emulsion oil solution, and it becomes droplet-like to be uniformly distributed.
5. method as claimed in claim 4, is characterized in that: in step (2), mixing speed is 200r/min.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733539A (en) * | 2016-05-10 | 2016-07-06 | 西南石油大学 | Compound gas hydrate anti-agglomerant and application thereof |
| CN108980623A (en) * | 2018-06-22 | 2018-12-11 | 东莞理工学院 | A kind of kinetic inhibition oil hydrosol and its preparation method and application of pair of hydrate response |
| CN109266312A (en) * | 2018-10-12 | 2019-01-25 | 中国石油大学(华东) | The preparation method and hydrate phase change refrigerating method and hydrate phase change refrigeration system of composition and heat transfer medium |
| CN110564472A (en) * | 2019-08-22 | 2019-12-13 | 湘南学院 | Method for inhibiting hydrate decomposition and hydrate storage and transportation method |
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| US5539021A (en) * | 1995-06-05 | 1996-07-23 | The Dow Chemical Company | Process for preparing high internal phase ratio emulsions and latexes derived thereof |
| CN102755847A (en) * | 2012-07-17 | 2012-10-31 | 山东大学 | Preparation method of water-in-oil nano-emulsion with low energy consumption |
| CN103028353A (en) * | 2012-12-14 | 2013-04-10 | 常州大学 | Degradable gas hydrate accelerant and preparation method thereof |
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2015
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| US5539021A (en) * | 1995-06-05 | 1996-07-23 | The Dow Chemical Company | Process for preparing high internal phase ratio emulsions and latexes derived thereof |
| CN102755847A (en) * | 2012-07-17 | 2012-10-31 | 山东大学 | Preparation method of water-in-oil nano-emulsion with low energy consumption |
| CN103028353A (en) * | 2012-12-14 | 2013-04-10 | 常州大学 | Degradable gas hydrate accelerant and preparation method thereof |
Non-Patent Citations (2)
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| DONG-LIANG ZHONG, ET AL.: "Methane recovery from coal mine gas using hydrate formation in water-in-oil emulsions", 《APPLIED ENERGY》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733539A (en) * | 2016-05-10 | 2016-07-06 | 西南石油大学 | Compound gas hydrate anti-agglomerant and application thereof |
| CN105733539B (en) * | 2016-05-10 | 2018-10-12 | 西南石油大学 | A kind of compound Anti-agglomerates of Gas Hydrate and its application |
| CN108980623A (en) * | 2018-06-22 | 2018-12-11 | 东莞理工学院 | A kind of kinetic inhibition oil hydrosol and its preparation method and application of pair of hydrate response |
| CN108980623B (en) * | 2018-06-22 | 2021-01-08 | 东莞理工学院 | Kinetic inhibition oil-water emulsion responding to hydrate and preparation method and application thereof |
| CN109266312A (en) * | 2018-10-12 | 2019-01-25 | 中国石油大学(华东) | The preparation method and hydrate phase change refrigerating method and hydrate phase change refrigeration system of composition and heat transfer medium |
| CN110564472A (en) * | 2019-08-22 | 2019-12-13 | 湘南学院 | Method for inhibiting hydrate decomposition and hydrate storage and transportation method |
| CN110564472B (en) * | 2019-08-22 | 2020-10-16 | 湘南学院 | Method for inhibiting hydrate decomposition and hydrate storage and transportation method |
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