CN107314247B - Environmental protection compound type hydrate polymerization inhibitor composition and application thereof - Google Patents
Environmental protection compound type hydrate polymerization inhibitor composition and application thereof Download PDFInfo
- Publication number
- CN107314247B CN107314247B CN201610411890.4A CN201610411890A CN107314247B CN 107314247 B CN107314247 B CN 107314247B CN 201610411890 A CN201610411890 A CN 201610411890A CN 107314247 B CN107314247 B CN 107314247B
- Authority
- CN
- China
- Prior art keywords
- hydrate
- polymerization inhibitor
- gas
- environmental protection
- compound type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
Landscapes
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Lubricants (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention relates to a kind of environmental protection compound type hydrate polymerization inhibitor composition and application thereof, mainly solve the problems, such as that environment easy to pollute, polymerization inhibition performance are unstable in the prior art, dosage is big.The present invention is by using a kind of environmental protection compound type hydrate polymerization inhibitor composition, with mass ratio it is that the compounding of 0.1~10:0.1~10:0.1~10 obtains and application thereof technical solution and preferably solves the above problem by polyol-based non-ionic surfactant, xanthan gum and synergist, can be used in oil-gas transportation.
Description
Technical field
The present invention relates to a kind of environmental protection compound type hydrate polymerization inhibitor compositions and application thereof.
Background technique
Gas hydrate is the non-stoichiometry formed under the conditions of cryogenic high pressure by certain gas molecules and hydrone
Crystal caged substance, is commonly referred to as combustible ice.In petroleum, the defeated process of gas extraction sum aggregate, due to its special high pressure and
Low temperature environment, various low-boiling hydro carbons such as methane, ethane, carbon dioxide and hydrogen sulfide be easy to in petroleum or natural gas
The water of carrying forms hydrate particle, and is easy to build up together, forms larger blocky tamper, can be blocked when serious pipeline,
The equipment such as pit shaft, valve and instrument, to oil and natural gas extracting, gathering it is defeated bring very big difficulty, from 1934
Hammersdhmidt find Hydrate Plugging natural gas line since, how in production of hydrocarbons and gathering line prevention and control be hydrated
Object blocking has become oil and gas industry circle urgent problem.
Conventional heat suppressing method and novel dynamic control method are specifically included that the preventing control method of hydrate at present.
Traditional thermodynamics suppressing method mainly passes through removing water phase, heating pipeline, decompression and hydrate thermodynamic inhibitor is added
The methods of come change system hydration thermodynamic formation condition, make pipe it is defeated during without gas hydrate synthesis.Dehydration technique is removing
System inner aqueous phase is more common method during current natural gas tube is defeated to prevent and treat the formation of hydrate.But very using the method
Difficulty eliminates pipeline inner aqueous phase completely, may locally have water phase, therefore still has larger blocking risk.Heating Pipeline approach is to mention
High system temperature makes it higher than corresponding hydrate under system pressure and generates temperature, to avoid blocking up caused by gas hydrate synthesis
Plug.Voltage drop method reduces line pressure, makes it below corresponding hydrate under system temperature and generates pressure, to avoid hydrate
It generates.But since pipeline delivery pressure cannot arbitrarily change under normal circumstances, it is larger which uses limitation.Addition
Hydrate thermodynamic inhibitor, such as methanol, ethylene glycol, the thermodynamical equilibrium condition for changing system hydrate (it is high to generate pressure
In pipeline delivery pressure or temperature is generated lower than pipeline delivery temperature), to avoid the formation of hydrate in pipeline.But the method presses down
Preparation dosage is larger, usually the 30%~50% of system water, higher cost, and easily pollutes the environment.
Novel dynamic control method mainly includes two class of hydrate dynamic inhibitor and hydrate polymerization inhibitor.Wherein, water
It closes object kinetic inhibitor and is generally some water-soluble high molecular polymers, it does not change the thermodynamical equilibrium of system hydrate
Condition, but it is adsorbed in hydrate particle surface, to prevent or delay the further growth of hydrate crystal grain, guarantee conveying
It does not block in the process.Hydrate polymerization inhibitor is some polymer and surfactant, exists simultaneously condition in water-oil phase
Lower just to can be used, it does not change the formation condition of hydrate, the formation of hydrate in permission system, but controllable hydrate particle
Size prevents the aggregation and deposition of hydrate particle, and making it finally is in stable slurry conveying.It finds, is hydrated in the course of the research
Object kinetic inhibitor rejection is influenced by system degree of supercooling, using limited under the conditions of compared with high supercooling degree.From can bear
Maximum subcooled temperature and practical application area (oil-gas-water multi-phase mixed delivering system) angle for, gas hydrate polymerization inhibitor has
Wider application prospect.
In terms of hydrate polymerization inhibitor exploitation, researcher has developed numerous hydrate polymerization inhibitors, such as french petroleum at present
A series of research institute in patents (EP594579, EP 323307 etc.) details large quantities of tables that can be used as hydrate polymerization inhibitor
Face activating agent mainly includes the amides compounds such as hydroxycarboxylic acid amide, alkoxy dihydroxy carboxylic acids amide.Chinese patent
A kind of hydrate polymerization inhibitor is proposed in CN102451640A " a kind of non-ionic composite hydrate polymerization inhibitor ", by polyoxyethylene two
Carboxylic acid lipid Shuangzi nonionic surfactant obtains after compounding with polyol-based non-ionic surfactant, and disadvantage is such resistance
Poly- agent additive amount is larger, and the hydrate slurry formed under the conditions of compared with high-moisture percentage is more sticky, and it is big to manage defeated pressure drag.It is Chinese special
One has been synthesized in sharp CN104262184A " gemini quaternary ammonium salt class polymerization inhibitor and its synthetic method and inhibition hydrate build up method "
Class has the gemini quaternary ammonium salt of hydrate polymerization inhibition performance, but it is organic synthesis product, biological degradability that disadvantage, which is such polymerization inhibitor,
And economic and environment-friendly property is poor, and additive amount is larger, and using limited in high-moisture percentage system.
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 unstable in the prior art, use
Big problem is measured, a kind of new environmental protection compound type hydrate polymerization inhibitor composition is provided, the composition has environmental protection, polymerization inhibition performance
Stablize, the advantage that dosage is small.The second technical problem to be solved by the present invention is to provide one kind and solves one of technical problem phase
The purposes of corresponding environmental protection compound type hydrate polymerization inhibitor composition.
One of in order to solve the above problem, The technical solution adopted by the invention is as follows: a kind of environmental protection compound type hydrate inhibits
Agent composition, including polyol-based non-ionic surfactant, xanthan gum and synergist, polyol type non-ionic surface active
The mass ratio of agent, xanthan gum and synergist is 0.1~10:0.1~10:0.1~10, the polyol type non-ionic surface active
Agent is Span series non-ionic surfactants, and the molecular structural formula of the xanthan gum is as follows:
The compounding synergist be ethyl alcohol, ethylene glycol, ether, diethylene glycol monobutyl ether, in dibutyl ethylene glycol ether at least
It is a kind of.
In above-mentioned technical proposal, it is preferable that the mass ratio of polyol-based non-ionic surfactant, xanthan gum and synergist
For 0.1~3:0.1~5:0.1~5.
In above-mentioned technical proposal, it is preferable that Span series polyol-based non-ionic surfactant be Span20,
At least one of Span40, Span60, Span65, Span80, Span85.
In above-mentioned technical proposal, it is preferable that xanthan gum is a kind of unit cell polysaccharide generated by pseudo xanthomonas fermentation, by
The black rotten xanthomonas campestris of wild cabbage is using carbohydrate as primary raw material, through aerobic fermentation biotechnology, cutting 1,6-
Glycosidic bond after opening branch, is bonded to a kind of acidic extracellular heteroglycan of acidity of straight chain composition in Isosorbide-5-Nitrae-.
In order to solve the above problem two, The technical solution adopted by the invention is as follows: a kind of environmental protection compound type hydrate inhibits
The purposes of agent 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%.
Compositional type hydrate polymerization inhibitor provided by the invention can effectively prevent the accumulation in grease system between hydrate particle,
Uniform and stable hydrate slurry is ultimately formed, can effectively solve the problems, such as Hydrate Plugging in oil-gas-water three-phase mixed transferring.This hair
The xanthan gum of bright use has good biological degradability, nontoxic, does not pollute the environment.In addition, provided by the invention multiple
Distribution type polymerization inhibitor also has many advantages, such as that dosage is low, economic and environment-friendly, polymerization inhibition performance is excellent, has a good application prospect, and 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, constant temperature air bath 2, temperature sensor 3 and pressure biographies
Sensor 4, hand push pump 5, stirring system and computer data automated collection systems 6.The maximum functional body of high-pressure sapphire reaction kettle
Product is 49cm3, maximum working pressure 50MPa, operating temperature range 183K-423K.A closed work is had in reaction kettle
Plug 7, can separate charging fluid (petroleum ether) with experimental system, and reacting kettle inner pressure can pump 5 by hand push and be adjusted.Separately
Outside, LGY150A type cold light source is configured with outside this sapphire 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 xanthan gum is present embodiments provided, which is by Span20, Huang
Virgin rubber 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 2]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span20, xanthan gum and ethyl alcohol
It compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 3]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span20, xanthan gum and ethyl alcohol
It compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 4]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span40, xanthan gum and ethyl alcohol
It compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 5]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span60, xanthan gum and ethyl alcohol
It compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 6]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span80, xanthan gum and ethyl alcohol
It compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 7]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span60, xanthan gum and second two
Alcohol compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 8]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span60, xanthan gum and second two
Alcohol compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 9]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span80, xanthan gum and ether
It compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 10]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span80, xanthan gum and diethyl
Glycol monobutyl ether compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 11]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span20, xanthan gum and diethyl
Dibutyl ether compounds 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
After have no that hydrate occur builds up agglomeration blocking, stirrer can freely move up and down in reaction kettle；After stopping stirring, it is possible to find gas
Gas hydrate is gradually deposited at reactor bottom, and upper layer is oily phase, and lower layer is hydrate phase, stops smoothly restart after stirring 12h,
Hydrate particle disperses again, still without the phenomenon that agglomerating is built up, so that it is good to illustrate that polymerization inhibitor provided in this embodiment has
Polymerization inhibition performance.
[embodiment 12]
A kind of Compositional type hydrate polymerization inhibitor containing xanthan gum is present embodiments provided, by Span60, xanthan gum and ethyl alcohol
It compounds 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 environmental protection compound type hydrate polymerization inhibitor composition, including polyol-based non-ionic surfactant, xanthan gum and
Synergist, the mass ratio of polyol-based non-ionic surfactant, xanthan gum and synergist be 0.1~10:0.1~10:0.1~
10, the polyol-based non-ionic surfactant is Span series non-ionic surfactants, the molecule knot of the xanthan gum
Structure formula is as follows:
The synergist is at least one of ethyl alcohol, ethylene glycol, ether, diethylene glycol monobutyl ether, dibutyl ethylene glycol ether.
2. environmental protection compound type hydrate polymerization inhibitor composition according to claim 1, it is characterised in that polyol type nonionic
The mass ratio of surfactant, xanthan gum and synergist is 0.1~3:0.1~5:0.1~5.
3. environmental protection compound type hydrate polymerization inhibitor composition according to claim 1, it is characterised in that Span series polyalcohol
Type nonionic surfactant is at least one of Span20, Span40, Span60, Span65, Span80, Span85.
4. environmental protection compound type hydrate polymerization inhibitor composition according to claim 1, it is characterised in that the xanthan gum is one
The unit cell polysaccharide that kind is generated by pseudo xanthomonas fermentation, by cabbage black rot xanthomonas campestris based on carbohydrate
Raw material is wanted, through aerobic fermentation biotechnology, 1,6- glycosidic bond is cut off, after opening branch, is being bonded to straight chain group by Isosorbide-5-Nitrae-
At a kind of acidic extracellular heteroglycan of acidity.
5. the purposes of environmental protection compound type hydrate polymerization inhibitor composition described in claim 1, in oil-gas transportation.
6. the purposes of environmental protection compound type hydrate polymerization inhibitor composition according to claim 5, it is characterised in that applicable oil-
The volume that air-water mixes water in defeated system is no more than the 50% of grease total volume, according to actual fed medium composition and locating operating condition
Condition, the addition quality for adjusting hydrate polymerization inhibitor is 0.1%~10% of water quality in system, oil-gas-water three-phase mixed transferring body
The temperature control of system is 248K~323K, and pressure control is 0.1MPa~50.0MPa.
7. the purposes of environmental protection compound type hydrate polymerization inhibitor composition according to claim 5, it is characterised in that hydrate resistance
The addition quality of poly- agent is 0.5%~5% of water quality in system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610411890.4A CN107314247B (en) | 2016-06-12 | 2016-06-12 | Environmental protection compound type hydrate polymerization inhibitor composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610411890.4A CN107314247B (en) | 2016-06-12 | 2016-06-12 | Environmental protection compound type hydrate polymerization inhibitor composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107314247A CN107314247A (en) | 2017-11-03 |
| CN107314247B true CN107314247B (en) | 2019-04-09 |
Family
ID=60185717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610411890.4A Active CN107314247B (en) | 2016-06-12 | 2016-06-12 | Environmental protection compound type hydrate polymerization inhibitor composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107314247B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817440B (en) * | 2020-06-18 | 2022-11-08 | 中国石油化工股份有限公司 | Compound hydrate accelerant, application and gas storage and transportation method |
| CN112877047B (en) * | 2021-01-27 | 2022-08-23 | 四川柏诗特能源科技有限公司 | Efficient prevention and control agent and process for solving low-temperature freezing and blocking of natural gas production pipeline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388201A (en) * | 2002-04-27 | 2003-01-01 | 华南理工大学 | Efficient composite hydrate anticoagulant |
| CN102451640A (en) * | 2010-10-18 | 2012-05-16 | 中国石油大学(北京) | Non-ionic compound hydrate anti-agglomerant |
| CN104390138A (en) * | 2014-09-18 | 2015-03-04 | 中国海洋石油总公司 | Compound gas hydrate polymerization inhibitor and application thereof |
-
2016
- 2016-06-12 CN CN201610411890.4A patent/CN107314247B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388201A (en) * | 2002-04-27 | 2003-01-01 | 华南理工大学 | Efficient composite hydrate anticoagulant |
| CN102451640A (en) * | 2010-10-18 | 2012-05-16 | 中国石油大学(北京) | Non-ionic compound hydrate anti-agglomerant |
| CN104390138A (en) * | 2014-09-18 | 2015-03-04 | 中国海洋石油总公司 | Compound gas hydrate polymerization inhibitor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107314247A (en) | 2017-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ding et al. | Rheology of natural gas hydrate slurry: Effect of hydrate agglomeration and deposition | |
| CN101675141B (en) | Treatment fluids comprising diutan and associated methods | |
| CN103865505B (en) | Non-ionic composite Anti-agglomerates of Gas Hydrate | |
| CN104390138B (en) | A kind of Compositional type gas hydrate polymerization inhibitor and its application | |
| CN108559479B (en) | Reverse microemulsion polymer fracturing liquid system capable of being constructed on line | |
| MXPA06011847A (en) | Gelled oil with surfactant. | |
| CN107314247B (en) | Environmental protection compound type hydrate polymerization inhibitor composition and application thereof | |
| CN108504346A (en) | A kind of antifreeze clean fracturing fluid and preparation method thereof | |
| CN105179942B (en) | A kind of Compositional type hydrate inhibitor | |
| CN104109518A (en) | Oil displacement composition used for low permeability oil reservoirs, and preparation method thereof | |
| Shi et al. | Anti-agglomeration evaluation and Raman spectroscopic analysis on mixed biosurfactants for preventing CH4 hydrate blockage in n-octane+ water systems | |
| CN105331348A (en) | Homogeneous-phase microemulsion oil-displacing agent applied to low-permeation oil field and preparation method of homogeneous-phase microemulsion oil-displacing agent | |
| CN110452677A (en) | One kind is based on modified MoS2The method for preparing drag reducer | |
| CN105733539B (en) | A kind of compound Anti-agglomerates of Gas Hydrate and its application | |
| CN107828402B (en) | Improve deep viscous crude CO2Chemical additive for recovery ratio in gas flooding process | |
| Yu et al. | Screening Hydrate Antiagglomerants for an Oil–Gas–Water System from Various Commercial Chemicals Using Rocking Cells | |
| CN107828401A (en) | One kind enhancing CO2Dissolve each other, reduce the oil driving additive of viscosity of crude with crude oil | |
| Jing et al. | Investigation of natural gas hydrate formation and slurry viscosity in non-emulsifying oil systems | |
| CN107314245B (en) | Compositional type hydrate polymerization inhibitor composition containing lecithin and application thereof | |
| CN107312513A (en) | Compositional type hydrate anticoagulant composition and application thereof | |
| Moradpour et al. | Controlling hydrate slurry transportability by optimizing anti-agglomerant usage in high water cut systems | |
| CN105179939B (en) | A kind of application of the hydrate anticoagulant of Compositional type containing rhamnolipid | |
| CN111500310A (en) | Crude oil composite demulsifier and preparation method thereof | |
| CN102451640B (en) | Non-ionic compound hydrate anti-agglomerant | |
| CN1048798C (en) | Viscosity-reducing paraffin inhibitor for high water-bearing oil well and gathering line and preparing process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |