CN107314245B - Compositional type hydrate polymerization inhibitor composition containing lecithin and application thereof - Google Patents
Compositional type hydrate polymerization inhibitor composition containing lecithin and application thereof Download PDFInfo
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F17D1/00—Pipe-line systems
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Abstract
The present invention relates to a kind of Compositional type hydrate polymerization inhibitor composition and application thereof containing lecithin, mainly solves the problems, such as that environment easy to pollute, polymerization inhibition performance are poor in the prior art, dosage is big.The present invention is by using a kind of Compositional type hydrate polymerization inhibitor composition containing lecithin, with mass ratio it is that the compounding of 0.1~5:0.1~10:0.1~10 obtains and application thereof technical solution and preferably solves the above problem by polyol-based non-ionic surfactant, lecithin zwitterionic surfactant and compounding synergist, can be used in oil-gas transportation.
Description
Technical field
The present invention relates to a kind of Compositional type hydrate polymerization inhibitor composition and application thereof containing lecithin.
Background technique
Certain gas molecules (such as CH4、CO2And H2S etc.) and hydrone a kind of non-chemical meter is easily formed under cryogenic high pressure
The crystal cage of amount property, frequently referred to combustible ice.During petroleum, natural gas extraction sum aggregate are defeated, low temperature locating for pipeline is high
Pressure ring border is very beneficial for the formation of hydrate particle, and when serious, these hydrates can block pit shaft, pipeline, valve and certain
Key equipment, to influence the development efficiency of natural gas, particularly with oil-gas-water multi-phase mixed delivering system, hydrate problems are more
Seriously.
The method that tradition solves Hydrate Plugging is mainly based upon the thermodynamic process of gas hydrate synthesis, and settling mode is main
Including water removal techniques, pipeline heating, decompression control, note thermodynamic inhibitor etc..Water removal techniques are to cause hydrate by removing
The hydrone of generation inhibits hydrate, but technique has certain limitation, and the water in pipeline is difficult thoroughly to eliminate, and
And the formation of hydrate is not absolutely necessary to the presence of free water phase, if hydrate nucleus or Free water be adsorbed in wall surface or
Elsewhere, although the water concentration in liquid hydrocarbon phase is very low, hydrate can also be easy to mutually grow from liquid hydrocarbon.Pipeline heats
It keeps system temperature to be higher than water-hydrate-gas three-phase equilibrium temperature under system pressure, thermally decomposes hydrate, avoid blocking up
Fill in pipeline；But the difficult point of the technology is to be difficult to position Hydrate Plugging position, pays attention to increasing because of temperature in heating process
And pressure is set to rise the safety problem generated, and the water decomposed must be driven off；Furthermore the curent change in electric heating can also cause
Corrosive pipeline problem needs to carry out sacrificing positive pole protection to the pipeline of heating.Note thermodynamic inhibitor mainly passes through injection
There are some alcohols, such as methanol, ethylene glycol destroy the hydrogen bond of hydrate to improve the formation condition of hydrate, to inhibit to be hydrated
The generation of object；Although present thermodynamic inhibitor is industrially widely used, since its Gao Chengben (is mainly reflected in dosage
Greatly, generally the 30%~50% of water) and influence to environment, there is an urgent need to find better inhibitor to substitute.
Past, as the alternative of conventional heat suppressing method, hydrate low-dosage inhibitor was over twenties years
Obtain greater advance.Low-dosage inhibitor includes two class of hydrate dynamic inhibitor and hydrate polymerization inhibitor.Hydrate power
Learning inhibitor is some water-soluble or aqueous dispersion polymers, they only inhibit the formation of hydrate in water phase, addition it is dense
It spends very low (usually 1% or so of water phase quality), it does not influence the thermodynamic condition of gas hydrate synthesis.Crystal of hydrate at
Core and early growth period, they are adsorbed in hydrate particle surface, and the cyclic structure of inhibitor passes through the crystal of hydrogen bond and hydrate
In conjunction with, delay the hydrate nucleation time or prevent crystal further growth, thus guarantee do not send out during transportation
Raw blocking, but its rejection is often influenced by system degree of supercooling, it is limited in the application of high supercooling degree system.Hydrate polymerization inhibitor is one
A little polymer and surfactant, inhibiting mechanism is different from kinetic inhibitor, mainly plays emulsifier, when water with
It just can be used in the presence of when oil is identical, hydrate polymerization inhibitor is added into system so that grease is mutually emulsified, by the moisture in oily phase
Small water droplet is dissipated into, although the small water droplet being emulsified in oily phase also generates hydrate at gas, the hydrate particle quilt generated
Solubilising is in micro emulsion, it is difficult to coalesce blocking, make it finally and be in stable slurry conveying, and the application effect of polymerization inhibitor is subcooled by system
Degree influence is smaller, and good inhibitory effect can be still played in high supercooling degree.Therefore, from the maximum subcooled temperature and reality that can be born
For application field (oil-gas-water multi-phase mixed delivering system), gas hydrate polymerization inhibitor has wider application prospect.
Based on this, researcher has developed numerous hydrate polymerization inhibitors at present, if French Petroleum Institute is a series of special
(EP594579, EP 323307 etc.) details large quantities of surfactants that can be used as hydrate polymerization inhibitor in benefit, mainly includes
The amides compounds such as hydroxycarboxylic acid amide, alkoxy dihydroxy carboxylic acids amide.Chinese patent CN104262184A " Shuangzi quaternary ammonium
Salt polymerization inhibitor and its synthetic method and inhibit hydrate to build up method " in synthesized and a kind of there are the double of hydrate polymerization inhibition performance
Sub- quaternary ammonium salt, but it is organic synthesis product that disadvantage, which is such polymerization inhibitor, and biological degradability and economic and environment-friendly property are poor, and additive amount
It is larger, and using limited in high-moisture percentage system.A kind of hydrate inhibitor is disclosed in Chinese patent CN101892038A,
It is made of the mixture of kinetic inhibitor and nitrate, acetate, such inhibitor is by inhibiting hydrate nucleation and growth
Mode carry out prevention and control hydrate, but it is affected by system degree of supercooling, and the salting liquid in inhibitor to conveyance conduit have compared with
Big corrosion risk.
Summary of the invention
The first technical problem to be solved by the present invention is that environment easy to pollute, polymerization inhibition performance are poor in the prior art, dosage is big
The problem of, a kind of new Compositional type hydrate polymerization inhibitor composition containing lecithin is provided, the composition has environmental protection, polymerization inhibitor property
The advantage that energy is excellent, dosage is small.The second technical problem to be solved by the present invention is to provide a kind of one of and solution technical problem
The purposes of the corresponding Compositional type hydrate polymerization inhibitor composition containing lecithin.
One of in order to solve the above problem, The technical solution adopted by the invention is as follows: a kind of Compositional type hydration containing lecithin
Object polymerization inhibitor composition, including polyol-based non-ionic surfactant, lecithin zwitterionic surfactant and compounding association
Same agent, polyol-based non-ionic surfactant, lecithin zwitterionic surfactant and compound synergist mass ratio be
0.1~5:0.1~10:0.1~10, the polyol-based non-ionic surfactant is by Span series non-ionic surfactants
It is formed with Tween series non-ionic surfactants, lecithin molecules are contained by glycerol, two fatty acid-based, phosphoric acid and one
The group of amino forms, and molecular structural formula isThe compounding
Synergist is at least one of ethyl alcohol, ethylene glycol, ether, diethylene glycol monobutyl ether, dibutyl ethylene glycol ether.
In above-mentioned technical proposal, it is preferable that polyol-based non-ionic surfactant, lecithin amphoteric ion surface-active
The mass ratio of agent and compounding synergist is 0.1~3:0.1~5:0.1~5.
In above-mentioned technical proposal, it is preferable that Span series non-ionic surfactants be Span20, Span40, Span60,
At least one of Span65, Span80, Span85；Tween series non-ionic surfactants be Tween20, Tween40,
At least one of Tween60, Tween65, Tween80, Tween85.
In above-mentioned technical proposal, it is preferable that Span series non-ionic surfactants and Tween series non-ionic surface are living
Property agent mass ratio be 1:1.
In order to solve the above problem two, The technical solution adopted by the invention is as follows: a kind of Compositional type hydration containing lecithin
The purposes of object polymerization inhibitor composition, in oil-gas transportation.
In above-mentioned technical proposal, it is preferable that it is overall that the volume that applicable oil-gas-water mixes water in defeated system is no more than grease
Long-pending 50%, according to actual fed medium composition and locating working condition, the addition quality for adjusting hydrate polymerization inhibitor is system
The 0.1%~10% of middle water quality, the temperature control of oil-gas-water three-phase mixed transferring system are 248K~323K, and pressure control is
0.1MPa~50.0MPa.
In above-mentioned technical proposal, it is preferable that the addition quality of hydrate polymerization inhibitor be system in water quality 0.5%~
5%.
Lecithin zwitterionic surfactant is all existing natural amphoteric surfactant, ovum in all organisms
Phospholipid molecule is made of glycerol, two fatty acid-based, phosphoric acid and an amino-containing group, and lecithin has emulsification well
And wettability, can be used in the case where temperature, pH value and salinity are in extreme situation, and nontoxic, can fast degraded biologically, avoid
Pollution to environment.In addition, its cavity effect, inoxidizability, flexibility and physiological characteristics are all preferable.
Compositional type hydrate polymerization inhibitor provided by the invention containing lecithin has good biodegradability, and can have
Effect prevents the aggregation in grease system between hydrate particle, controls hydrate particle size, efficiently solves oil-gas-water multiphase
Mix defeated middle Hydrate Plugging problem.In addition, the Compositional type hydrate polymerization inhibitor provided by the invention containing lecithin also has dosage
It the advantages that low, economic and environment-friendly, polymerization inhibition performance is excellent, has a good application prospect, achieves preferable technical effect.
Detailed description of the invention
Fig. 1 is high-pressure sapphire reaction kettle structural schematic diagram；
Fig. 2 is the online granulometry apparatus structure schematic diagram of PVM/FBRM；
In Fig. 1 and Fig. 2,1 high pressure jewel kettle autoclave body；2 air baths；3 temperature sensors；4 pressure sensors；5 hand push pump；6
Automatic data acquisition system；7 pistons；8 stirrers；9 magnet；10FBRM probe；11 autoclaves；12 temperature data collecting systems；
13 pressure data acquisition systems；14 pressure sensors；15 water-baths；16PVM probe；17 temperature sensors.
It in moisture content is hydrate in 10% (diesel oil+water+natural gas) system that Fig. 3, which is the polymerization inhibitor that provides of embodiment 12,
It is formed after stablizing, the picture shot by PVM/FBRM；
It in moisture content is gas water in 10% (diesel oil+water+natural gas) system that Fig. 4, which is the polymerization inhibitor that provides of embodiment 12,
Close particle chord length distribution situation of change in object generating process.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
Comparative example 1
This comparative example and other specific embodiments are all made of high-pressure sapphire reaction kettle and carry out system evaluation, structural representation
Figure is as shown in Figure 1.The device mainly includes high-pressure sapphire reaction kettle body 1, air bath 2, temperature sensor 3 and pressure sensors
4, hand push pump 5, stirring system and automatic data acquisition system 6.The maximum functional volume of high-pressure sapphire reaction kettle is 49cm3,
Maximum working pressure is 50MPa, operating temperature range 183K-423K.An Air-tight piston 7 is had in reaction kettle, can will be increased
Pressure fluid (petroleum ether) is separated with experimental system, and reacting kettle inner pressure can pump 5 by hand push and be adjusted.In addition, this sapphire
LGY150A type cold light source is configured with outside reaction kettle.
Carrying out applicating evaluating experiment using above-mentioned high-pressure sapphire reaction kettle, specific step is as follows:
(1) after to the cleaning of entire experimental system, configuration is placed in containing grease system 15mL described in this comparative example (embodiment)
In sapphire reaction kettle body 1, system temperature is set as 274.2K, i.e. experimental temperature；
(2) after reactor temperature reaches preset value and stablizes lasting 4h, system is vacuumized, and be passed through experimental gas
Displacement 3 times (experimental gas composition as shown in table 1) continues to be passed through a certain amount of experimental gas making up to dissolution equilibrium
(gas flow poured makes gas pressure when balance be less than corresponding hydrate equilibrium pressure at a temperature of this)；
(3) being passed through experimental gas to system pressure is 7.2MPa i.e. experimental pressure, closes intake valve, opens blender, whole
A experimentation mixing speed is invariable；With the progress of reaction, gas is constantly consumed, and to keep system initial pressure, is pushed away
Starting to push away 5 change reaction system volumes of pump makes its keep constant pressure, and records hand push and pump 5 degrees to calculate gas consumption volume, together
When observation system in gas hydrate macroscopic form variation, system temperature, pressure and reaction time is all made of computer data
Automated collection systems 6 record；
(4) experimental pressure is stablized and after continuous service 12h, stops stirring 12h and restarts, investigates the stopping transportation of hydrate slurry
When restarting whether blockage phenomenon, after restarting stable operation 4h, take top tank air carry out chromatography, according to gas composition from
And practical degree of supercooling is calculated, degree of supercooling is equilibrium temperature (the equilibrium temperature Chen- of gas hydrate under identical experiment pressure
Guo model calculate) and experimental temperature difference；
(5) regulating system temperature is 303K, after gas hydrate decomposes completely in reaction kettle, restarts the following group experiment.
In this comparative example, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), this comparative example is not added any kind of
Hydrate inhibitor.
Table 1 tests the composition of simulation natural gas used
Experimental phenomena when hydrate polymerization inhibitor can effectively prevent gas hydrate from building up agglomeration are as follows: in experimental temperature and pressure
Under the conditions of power, the hydrate particle formed in experimentation is dispersed in oily phase, and system is distributed in slurry, and no hydrate is poly-
Caking phenomenon is accumulated, the stirrer in reaction kettle can stablize free up and down motion, still can smoothly restart after stopping stirring 12h, in kettle
Without appearance agglomeration clogging.
Since any kind of hydrate inhibitor not being added in this comparative example, be passed through gas pressure to test pressure
After power is less than 20min, both occur hydrate particle in grease system, and quickly assemble, while starting in kettle wall and bottom
It is a large amount of to deposit, it is blocked after 2min, stirrer can not freely move up and down, to illustrate, any inhibitor body is not added
The grease system of system easily blocks under experimental temperature and pressure condition.
Comparative example 2
According to condition described in comparative example 1, in this comparative example, in reaction kettle grease system by 3.0ml deionized water and
- 20# diesel oil the composition of 12ml, i.e. moisture content are the grease system of 20% (calculating on the basis of the sum of volume of Yi Shui and oil), this
Any kind of hydrate inhibitor is not added for comparative example, is evaluated using high-pressure sapphire reaction kettle described in comparative example 1,
Specific experiment process is as described in comparative example 1.
Since any kind of hydrate inhibitor is not added in this comparative example, gas pressure is being passed through to experimental pressure
After 5min, both occur hydrate particle in grease system, and quickly assemble, while starting largely in kettle wall and bottom
It deposits, is blocked after 1min, stirrer can not freely move up and down, to illustrate, any inhibitor system is not added
Grease system easily blocks under experimental temperature and pressure condition.
Comparative example 3
According to condition described in comparative example 1, this comparative example provides independent Span20 as hydrate polymerization inhibitor, using pair
High-pressure sapphire reaction kettle described in ratio 1 is evaluated, and specific experiment process is as described in comparative example 1.
In this comparative example, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of this comparative example
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
Incipient stage after the air inlet of this comparative example, hydrate particle are still scattered in oily phase, but as hydrate is raw
At the increase of amount, hydrate particle starts to assemble, and is gradually deposited on bottom, then occur Severe blockage phenomenon, stirrer without
Method freely moves up and down, and thus illustrates, independent Span20 not can effectively prevent the accumulation between hydrate particle in this comparative example, resistance
Poly- performance is poor.
Embodiment 1
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, which is by (Span20+
Tween60), lecithin and ethyl alcohol compound to obtain with quality 1:1:1.
Above-mentioned Compositional type hydrate polymerization inhibitor is applied to moisture content (to count on the basis of the sum of volume of Yi Shui and oil for 10%
Calculate) grease system, and the using effect of the Compositional type hydrate polymerization inhibitor of the present embodiment is evaluated, the present embodiment uses
High-pressure sapphire reaction kettle described in comparative example 1 is evaluated, and specific experiment process is as described in comparative example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water in system.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 2
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span20+Tween60), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 0.5:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 3
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span20+Tween60), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 0.5:1:3.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 4
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span20+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 5
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span60+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 6
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span60+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 3.0ml deionized water and 12ml in reaction kettle, that is, is contained
Water rate is the grease system of 20% (calculating on the basis of the sum of volume of Yi Shui and oil), and the additive amount of the polymerization inhibitor of the present embodiment is
The 1.0% of water quality in system, the experimental gas composition being passed through are shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 7
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span60+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 4.5ml deionized water and 10.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 30% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 8
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span60+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 6.0ml deionized water and 9.0ml in reaction kettle, i.e.,
Moisture content is the grease system of 40% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 9
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span80+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 10
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span80+Tween40), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 11
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span20+Tween85), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
The present embodiment is evaluated using high-pressure sapphire reaction kettle described in comparative example 1, and specific experiment process is as compared
Described in example 1.
In the present embodiment, grease system is made of the -20# diesel oil of 1.5ml deionized water and 13.5ml in reaction kettle, i.e.,
Moisture content is the grease system of 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the additive amount of the polymerization inhibitor of the present embodiment
It is 1.0% of water quality in system, the experimental gas composition being passed through is shown in Table 1.
In the whole experiment process of the present embodiment, gas hydrate particle is dispersed in oily phase, continuous operation 12h
Do not occur hydrate afterwards and build up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Hydrate is gradually deposited in reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h, water
Polymer beads disperse again, still without the phenomenon that agglomerating is built up, to illustrate that polymerization inhibitor provided in this embodiment has good resistance
Poly- performance.
Embodiment 12
A kind of Compositional type hydrate polymerization inhibitor containing lecithin is present embodiments provided, by (Span60+Tween80), ovum
Phosphatide and ethyl alcohol compound to obtain with quality 1:1:1.
By above-mentioned non-ionic composite gas hydrate polymerization inhibitor be applied to moisture content be 10% (Yi Shui and oil volume it
Calculated on the basis of) grease system in, and measure form of the gas hydrate in forming process and particle size distribution rule
Rule.
In order to investigate under Compositional type hydrate polymerization inhibitor existence condition of the invention, gas hydrate synthesis mistake in grease system
Metamorphosis and particle size distribution rule, the present embodiment in journey are being equipped with online particle laser visual analyzer PVM
(Particle video microscope) measuring probe 9 and online focused beam reflection measurement instrument FBRM (Focused beam
Reflectance measurement) measuring probe 10 autoclave 11 in tested, structural schematic diagram such as Fig. 2
It is shown.The device mainly includes: band water-bath and churned mechanically autoclave 11, PVM measuring probe 9/FBRM measuring probe
10 and relevant connection device and data collection system.11 material of autoclave is stainless steel material, can bear maximum pressure
32MPa, the effective volume of autoclave 11 are 534.72mL (internal diameter 51.84mm, the high 297.32mm of kettle)；Water bath with thermostatic control operation
Temperature range is 253K-323K；Mechanical stirring is made of the components such as motor and kettle inner impeller, is made anti-in autoclave 11
System is answered to be uniformly mixed.
Wherein PVM measuring probe 9 is made of six beam laser, illuminates probe front region (1680 μ ms by laser beam
1261 μm), and then shoot micromorphology variation in visible area.FBRM measuring probe 10 is equally measured by transmitting laser,
It emits near-infrared wavelength and is transferred to probe end by optical fiber, and probe end has the optical lens of a rotation that can make light
Deflection in experimentation, will reflect when the laser scanning of transmitting is to the surface of particle, chord length by measure reflection when
Between determine with the scanning speed of laser.In measurement process the experimental demand of laser scanning speed can 2~16m/s it
Between be adjusted.Quantity by the sapphire form drop measured in a certain time interval or particle chord length before probe is logical
It crosses statistics and obtains chord length distribution.
Tested that specific step is as follows using above-mentioned autoclave:
(1) before experiment starts, autoclave 11 and all connecting components are rinsed with cleaning solution, are blown with nitrogen
It is dry.PVM measuring probe 9 and FBRM measuring probe 10 are cleaned, is installed after reaching measurement request；
(2) the hydrate polymerization inhibitor of the 220mL grease system and the present embodiment configured in advance is injected into autoclave 11,
The air being dissolved in solution by vacuumizing venting；
(3) FBRM measuring probe 9, PVM measuring probe 10, temperature data collecting system 12 and pressure data acquisition system are opened
System 13, water-bath is adjusted to experimental temperature 274.2K, starts to cool down, and opens stirring, revolving speed 1000r/min, turn-on data acquisition system
System；
(4) after the temperature in autoclave 11 reaches experimental temperature and keeps 4h, stop stirring, be passed through gas to experiment
Pressure is 7.0MPa, and observes gas hydrate forming process metamorphosis and particle size distribution changing rule；
(5) after gas hydrate synthesis is stablized in autoclave 11, restart after stopping stirring 2h, observation stops stirring to hydration
The influence of object slurries；
(6) bath temperature is adjusted to 303K, and after decomposition of hydrate, exhaust drain restarts the following group experiment.
In the present embodiment, in autoclave 11 grease system by 22ml deionized water and 198ml -20# diesel oil group
At that is, moisture content mixes defeated system for 10% (calculating on the basis of the sum of volume of Yi Shui and oil), the polymerization inhibitor of the present embodiment
Additive amount is 1.0% of water quality in system, and gas phase used is simulation natural gas, and gas composition is as shown in table 1.
In the present embodiment experimentation, with the formation of gas hydrate in system, Fig. 3 is the system in this implementation
In, uniform hydrate slurry is ultimately formed as shown in Figure 3 by the picture of PVM shooting when generating gas hydrate completely.
Fig. 4 is the hydrate slurry particle chord length distribution situation of change measured by FBRM, with the shape of hydrate in experimentation
At gas hydrate particle size shifts to bulky grain size in system, but as experiment carries out, gas hydrate particle
Size tends towards stability, and after stopping stirring, due to the density contrast of hydrate phase and oily phase, hydrate particle sedimentation phenomenon occurs, but
After stirring is restarted, hydrate particle can be uniformly dispersed again, and no appearances blocking caking phenomenon at two (without there is gas on popping one's head in
The viscous wall of gas hydrate), to illustrate that the polymerization inhibitor of the present embodiment has good polymerization inhibition performance.
Claims (7)
1. a kind of Compositional type hydrate polymerization inhibitor composition containing lecithin, including polyol-based non-ionic surfactant, ovum
Phosphatide zwitterionic surfactant and compounding synergist, polyol-based non-ionic surfactant, lecithin amphoteric ion table
The mass ratio of face activating agent and compounding synergist is 0.1~5:0.1~10:0.1~10, and the polyol type non-ionic surface is living
Property agent is made of Span series non-ionic surfactants with Tween series non-ionic surfactants, lecithin molecules be by
Glycerol, two fatty acid-based, phosphoric acid and an amino-containing group composition, molecular structural formula areThe compounding synergist is ethyl alcohol, ethylene glycol, ether, two
At least one of ethyl alcohol monobutyl ether, dibutyl ethylene glycol ether.
2. the Compositional type hydrate polymerization inhibitor composition containing lecithin according to claim 1, it is characterised in that polyol type
The mass ratio of nonionic surfactant, lecithin zwitterionic surfactant and compounding synergist is 0.1~3:0.1~5:
0.1~5.
3. the Compositional type hydrate polymerization inhibitor composition containing lecithin according to claim 1, it is characterised in that Span series
Nonionic surfactant is at least one of Span20, Span40, Span60, Span65, Span80, Span85；Tween
Series non-ionic surfactants be Tween20, Tween40, Tween60, Tween65, Tween80, Tween85 at least
It is a kind of.
4. the Compositional type hydrate polymerization inhibitor composition containing lecithin according to claim 1, it is characterised in that Span series
Nonionic surfactant and the mass ratio of Tween series non-ionic surfactants are 1:1.
5. the purposes of the Compositional type hydrate polymerization inhibitor composition described in claim 1 containing lecithin, in oil-gas transportation.
6. the purposes of the Compositional type hydrate polymerization inhibitor composition containing lecithin according to claim 5, it is characterised in that suitable
The volume that oil-gas-water mixes water in defeated system is no more than the 50% of grease total volume, according to actual fed medium composition and institute
Locate working condition, the addition quality for adjusting hydrate polymerization inhibitor is 0.1%~10% of water quality in system, oil-gas-water three-phase
The temperature control for mixing defeated system is 248K~323K, and pressure control is 0.1MPa~50.0MPa.
7. the purposes of the Compositional type hydrate polymerization inhibitor composition containing lecithin according to claim 5, it is characterised in that water
The addition quality for closing object polymerization inhibitor is 0.5%~5% of water quality in system.
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