KR101956354B1 - A gas hydrate inhibitor having temperature-sensible and manufacturing method thereof - Google Patents
A gas hydrate inhibitor having temperature-sensible and manufacturing method thereof Download PDFInfo
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- KR101956354B1 KR101956354B1 KR1020170064128A KR20170064128A KR101956354B1 KR 101956354 B1 KR101956354 B1 KR 101956354B1 KR 1020170064128 A KR1020170064128 A KR 1020170064128A KR 20170064128 A KR20170064128 A KR 20170064128A KR 101956354 B1 KR101956354 B1 KR 101956354B1
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Abstract
The present invention relates to a composition for suppressing the formation of gas hittites which has a temperature responsive function and is easily recovered at a specific temperature or higher, and to a method for preparing the composition. More particularly, the present invention relates to t- (NIPAAm) as a monomer and having a polydispersity index (PDI) of 1.1 to 1.8; And a solvent, wherein the composition has a lower critical solution temperature (LCST) of 10 to 28 DEG C, and a composition for inhibiting gas hydrate formation. The composition for inhibiting gas hydrate formation according to the present invention is present in a liquid phase at a specific temperature or lower to inhibit the formation of gas hydrate and is present in a solid state at a specific temperature or higher and can be easily recovered. . In addition, the lower limit critical solution temperature (LCST) can be controlled by controlling the monomer ratio of the copolymer included in the composition, so that it can be manufactured to suit each crude oil or natural gas production environment.
Description
The present invention relates to a composition for suppressing the formation of a gas heattreate having a temperature responsive function and being easily recovered at a specific temperature or higher, and a method for producing the same.
When transporting gas or crude oil from a production well to a processing plant through a production well in a gas or oil production process, sediments such as wax, hydrate, asphaltene, etc., Which is a serious problem that hinders the flow of water.
For example, the gas hydrate is a kind of inclusion compound, which is a stable compound in which a gas molecule existing in a natural gas is physically bonded and formed in a cavity formed by water molecules under high pressure and low temperature conditions Crystal. It is known that more than 100 gas molecules form hydrate because the hydrate formers or the gas molecules of the object molecules are trapped in the solid phase lattice of the water molecules which are hydrogen-bonding molecules under the conditions of low temperature and high pressure. Since the above-mentioned gas hydrate is generally formed in an atmosphere of low temperature and high pressure, generation of the gas hydrate is not a serious problem in the atmosphere where the normal temperature and normal pressure are maintained.
However, in the case of the deep sea at low temperature and high pressure, or at the production facility of the offshore oil-gas field where high pressure is maintained, the environment where the gas hydrate is generated naturally is formed, and as a result, gas hydrate is generated at an undesired place . In particular, in the case of the oil and gas industry, a pipe pipe for collecting and transporting oil or gas from the deep sea is placed for a long time under a low-temperature and high-pressure environment in the sea, and a low-molecular- The gases react with water and the like to form a solid state gas hydrate. As described above, the gas hydrate formed on the pipe pipe or the like blocks the pipe pipe to obstruct the transfer of the production fluid. A great deal of effort has been made to suppress the formation of the precipitate in the oil and gas industry, and many inhibitors have been developed, since the once-occurring precipitate takes a lot of cost and time to remove and the work is stopped during the removal of the precipitate .
However, existing sediment inhibitors required a large amount of inhibitor because the sediment inhibitor had to be delivered throughout the production line. This method uses an excess of inhibitor, which necessitates additional separation steps in the future, resulting in high costs and environmental problems. In addition, simultaneous infusion of various inhibitors may result in reduced inhibitor efficiency due to cross-contamination between inhibitors. In addition, low dose inhibitors developed to overcome this problem have been developed, but these inhibitors are difficult to recover because they are dissolved in water.
An object of the present invention is to provide a composition for inhibiting the formation of gas hydrates, which exhibits a sufficient gas hydrate formation inhibiting effect while using a small amount of inhibitor and is easily recovered from crude oil or the like which has been transported, and a method for producing the same.
Another object of the present invention is to provide a method for inhibiting gas hydrate generation using the composition for inhibiting gas hydrate formation.
In order to achieve the above object, the present invention provides a thermosensitive recording medium which is synthesized by using t-butyl acrylamide (tBAAm) and N-isopropylacrylamide (NIPAAm) as monomers and has a polydispersity index (PDI) Wherein the composition has a lower limit critical solution temperature (LCST).
In order to accomplish the above object, the present invention provides a process for producing a reversible additive chain transfer (RAFT) using t-butyl acrylamide (tBAAm), N-isopropylacrylamide (NIPAAm) and a chain transfer agent. addition-fragmentation chain transfer) polymerization; And synthesizing a poly (tBAAm-co-NIPAAm) block copolymer by removing the chain transfer agent bound to the terminal of the polymerized polymer.
According to another aspect of the present invention, there is provided a method for inhibiting gas hydrate production using a composition for inhibiting gas hydrate formation.
The composition for inhibiting gas hydrate formation according to the present invention is present in a liquid phase at a specific temperature or lower to inhibit the formation of gas hydrate and is present in a solid state at a specific temperature or higher and can be easily recovered. . Further, since the lower limit critical solution temperature (LCST) can be controlled by controlling the monomer ratio in the synthesis of the thermosensitive copolymer contained in the composition, it is possible to manufacture the thermosensitive copolymer to be suitable for each crude oil or natural gas production environment.
FIG. 1 shows a reaction scheme for a synthesis process of a synthesized copolymer according to an embodiment of the present invention.
2 shows the results of 1 H-NMR analysis of the copolymer synthesized according to Examples 1 to 3. ((a) Example 1, (b) Example 2, (c) Example 3)
Fig. 3A shows the results of SEC analysis of the copolymer synthesized according to Example 2. Fig.
Fig. 3B shows the results of SEC analysis of the copolymer synthesized according to Example 3. Fig.
4 is a comparison of SEC analysis results of the copolymers synthesized according to Example 3 and Comparative Example 4.
5 is a photograph of a phase change in LCST of a composition for inhibiting gas hydrate production produced according to an embodiment of the present invention.
6A is a graph comparing UV-Visible analysis results of the composition for inhibiting gas hydrate formation produced according to Examples 1 and 4. FIG.
FIG. 6B is a graph comparing UV-Visible analysis results of the compositions for inhibiting gas hydrate formation according to Examples 2 and 5. FIG.
FIG. 6C is a graph comparing UV-Visible analysis results of the compositions for inhibiting gas hydrate formation according to Examples 3 and 6. FIG.
FIG. 7 shows UV-Visible analysis results of compositions for inhibiting the formation of gas hydrates produced according to Example 6 and Comparative Example 4. FIG.
8 is a schematic diagram of a high pressure autoclave reaction system for assessing the performance of gas hydrate inhibition in an embodiment according to the present invention.
FIG. 9A shows the results of evaluating methane hydrate formation inhibition performance of the compositions for inhibiting gas hydrate production produced according to Examples 1 to 6. FIG.
FIG. 9B shows the evaluation results of inhibition of methane hydrate formation by the compositions prepared according to Comparative Examples 1 to 3. FIG.
The present invention relates to a composition for suppressing the formation of a gas heattreate having a temperature responsive function and being easily recovered at a specific temperature or higher, and a method for producing the same.
FIG. 1 schematically shows a reaction process for synthesizing a poly (tBAAm-co-NIPAAm) block copolymer using t-butyl acrylamide (tBAAm) and N-isopropylacrylamide (NIPAAm) as monomers. Hereinafter, the present invention will be described with reference to Fig.
According to an aspect of the present invention there is provided a process for the preparation of reversible addition chain transfer (RAFT) using t-butyl acrylamide (tBAAm), N-isopropylacrylamide (NIPAAm), chain transfer agent, -fragmentation chain transfer) polymerization; Synthesizing a poly (tBAAm-co-NIPAAm) block copolymer by removing the chain transfer agent bound to the terminal of the polymerized polymer; And mixing the synthesized copolymer with a solvent to prepare a composition for inhibiting gas hydrate formation.
In order to synthesize the poly (tBAAm-co-NIPAAm) block copolymer according to the present invention, t-butyl acrylamide (tBAAm) and N-isopropylacrylamide (NIPAAm) are used as monomers.
The hydrophobic t-butylacrylamide has the ability to inhibit the formation of gas hydrate, and the poly-N-isopropylacrylamide has a lower critical solution temperature (LCST) of about 32 ° C in an aqueous solution as a thermosensitive polymer. The thermosensitive polymer is a material in which the phase transition is reversible depending on the rapid solubility difference of the polymer in the aqueous solution. The thermosensitive polymer can be divided into two types depending on the temperature change. That is, the material can be classified into a material having a lower critical solution temperature (LCST) and a material having an upper critical solution temperature (UCST). Among them, a substance having LCST has a hydrophobic property at a temperature higher than LCST Phase separation occurs.
When t-butylacrylamide, which is a hydrophobic monomer having gas hydrate formation inhibition ability, is synthesized with a hydrophilic monomer N-isopropylacrylamide as a copolymer, it can be easily dissolved in water at a low temperature condition where gas hydrate formation mainly occurs It is possible to synthesize a hydrophilic copolymer. The poly (tBAAm-co-NIPAAm) block copolymer synthesized in this way has a lower critical solution temperature (LCST) and dissolves in water at a temperature below the LCST to inhibit gas hydrate formation. It is possible to recover.
To synthesize a poly (tBAAm-co-NIPAAm) block copolymer having a desired LCST, the weight ratio of t-butylacrylamide and N-isopropylacrylamide monomer can be controlled. As the content of t-butylacrylamide monomer increases, the LCST of the synthesized poly (tBAAm-co-NIPAAm) block copolymer decreases. That is, since the LCST of the synthesized copolymer can be controlled by controlling the weight ratio of the monomers, a copolymer suitable for various crude oil or natural gas production environments can be successfully synthesized.
butyl acrylamide and N-isopropylacrylamide monomer may be mixed in a weight ratio of 1: 1.5 to 30, preferably in a weight ratio of 1: 1.5 to 25, more preferably in a weight ratio of 1: 1.5 to 20 ≪ / RTI > When such a weight ratio is satisfied, a copolymer having an LCST suitable for a crude oil or natural gas production environment can be synthesized, which is preferable.
The thermosensitive copolymer synthesized according to the present invention is characterized in that it is synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization.
Generally, a polymer compound synthesized by a radical polymerization reaction has a problem in that it can not have a constant molecular weight due to a large side reaction due to high reactivity of radicals. However, the RAFT polymerization reaction is a polymerization process in which each chain is uniformly grown and polydispersity index (PDI) is brought close to 1 by using a chain transfer called a 'RAFT agent' as a living radical polymerization reaction to be.
First, the step of performing a reversible addition fission chain transfer polymerization reaction using t-butyl acrylamide, N-isopropylacrylamide and a chain transfer agent will be described.
This is a reaction corresponding to 'Step 1' of FIG. 1, and the chain transfer agent used in the present invention is not particularly limited as long as it can cause a reversible radical formation reaction. Specifically, 4-cyano- 2-cyanomethyl-S-dodecyltrithiocarbonate}, 2-cyanomethyl-S-dodecyltrithiocarbonate}, 2-thiomethyl- Methyl-N-phenyldithiocarbamate, 2-cyanoprop-2-yl-dibenzoate, 2-cyanoprop- dithiobenzoate}, 2- (2-cyanoprop-2-yl) -S-dodecyltrithiocarbonate, 2- (Thiobenzoylthio) pentanoic acid, S, S-dibenzyltrithiocarbonate and 2-methyl-2 - [(dodecylsulfanyl) Tiokabo ) Sulfanyl] propanoic acid - but the like {2-Methyl-2 [(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid}, but is not limited to such. In a preferred embodiment of the present invention, the chain transfer agent is selected from the group consisting of 2-methyl-2 - [(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid {2-Methyl-2 - [(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid} .
The initiator used in the RAFT polymerization reaction according to the present invention is not particularly limited as long as it initiates a radical reaction. Specifically, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), 2,2'-azobis- (2,4-dimethyl valeronitrile), di-tert-butyl peroxide (DTBP), and the like may be used, but the present invention is not limited thereto. In one preferred embodiment of the present invention, the initiator may be AIBN.
The polymers polymerized according to the RAFT polymerization reaction require a reaction to remove them because the chain transfer agent is bonded to the terminals. This is a reaction corresponding to 'Step 2' in FIG. 1, and the reagent used therein is not particularly limited as long as it can remove chain transfer and is selected from organotin hydride and indium hydrides (AIBN), benzoyl peroxide (BPO), 2,2'-azobis- (2,4-dimethylvaleronitrile) (2,2'-azobis- -dimethyl valeronitrile) and di-tert-butyl peroxide (DTBP) may be used, but the present invention is not limited thereto. As a preferred embodiment of the present invention, tributyltin hydride and AIBN can be used.
The thermosensitive copolymer thus synthesized can be represented by the following formula (1), wherein the number average molecular weight (M n ) satisfies the range of 25,000 to 40,000 and the weight average molecular weight (M w ) satisfies the range of 33,000 to 45,000 .
[Chemical Formula 1]
(Wherein n is an integer of 12 to 133 and m is an integer of 255 to 266)
Further, the thermosensitive copolymer synthesized according to the present invention is the dispersion index [PDI = M w (weight-average molecular weight) / M n (number average molecular weight) is may be characterized in that 1.1 to 1.8, preferably 1.1 to 1.6, and more preferably 1.1 to 1.4. The low polydispersity index means that a copolymer having a narrow and uniform molecular weight distribution is synthesized. When the polydispersity index satisfies the above range, the temperature sensitivity to the phase change of the copolymer is improved near the LCST, So that it can have sensitivity characteristics.
The composition for inhibiting gas hydrate formation according to the present invention can be prepared by adding the thermosensitive copolymer to a solvent. Wherein the solvent is selected from the group consisting of distilled water, C 4 to C 6 alcohols, C 4 to C 6 glycols, C 4 to C 10 ethers, C 3 to C 10 esters, C 3 to C 10 ketones, And preferably distilled water or an aqueous solution of ethylene glycol (EG) can be used.
The composition for inhibiting gas hydrate formation according to the present invention can be prepared by adding the thermosensitive copolymer to distilled water. The thermosensitive copolymer added at this time may be added in an amount of 0.1 to 3.0% by weight, preferably 0.5 to 2.5% by weight, more preferably 0.8 to 2.0% by weight based on the total composition. If the content of the thermosensitive copolymer is less than 0.1% by weight, the effect of inhibiting the formation of gas hydrate becomes insufficient. If the content of the thermosensitive copolymer exceeds 3.0% by weight, the efficiency as a low-capacity inhibitor becomes low.
The LCST of the composition for inhibiting gas hydrate formation can be characterized by an LCST of 10 to 28 ° C. The LCST of the composition for inhibiting gas hydrate formation can be adjusted by controlling the monomer ratio of the thermosensitive copolymer to be added, Can be adjusted appropriately.
The composition for inhibiting gas hydrate formation according to the present invention can be prepared by adding the thermosensitive copolymer to an aqueous solution of ethylene glycol. Ethylene glycol is one of the thermodynamic inhibitors used to inhibit gas hydrate formation, and can exhibit a synergistic effect when used in combination with the thermosensitive copolymer according to the present invention.
The concentration of the aqueous ethylene glycol solution may range from 0.1 to 30% by weight, preferably from 1 to 20% by weight, more preferably from 5 to 15% by weight. If the concentration of the aqueous ethylene glycol solution exceeds 30% by weight, it takes a lot of time and cost to remove it.
The composition for inhibiting the formation of gas hydrate containing ethylene glycol according to the present invention can be characterized by having an LCST of 4 to 23 ° C. The LCST can be prepared by controlling the monomer ratio of the thermosensitive copolymer to be added or by adding an aqueous ethylene glycol solution By adjusting the concentration of the < / RTI >
According to another aspect of the present invention, there is provided a method of inhibiting gas hydrate production using a composition produced according to the present invention. The composition for inhibiting the formation of the gas hydrate produced according to the present invention can be prevented or delayed by adding it to the place where it is desired to prevent or delay gas hydrate generation and then the composition recovered in the solid phase at a temperature above the LCST is recovered So that the separation process can be completed easily.
Hereinafter, the present invention will be described in more detail with reference to Examples.
It is to be understood by those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention.
<Examples>
Example 1 (tBAAm: NIPAAm = 9:16)
20 ml of DMF was added to a reaction vessel equipped with a stirrer, a thermometer and a condenser. 2.51 g and 3.97 g of tBAAm and 3.9 g of NIPAAm were added, respectively, and 2-methyl-2 - [(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid and 0.0113 g of AIBN were added thereto, and then subjected to RAFT copolymerization at 80 DEG C for 24 hours to obtain poly (tBAAm-co-NIPAAm) -TTC.
The copolymerized poly (tBAAm-co-NIPAAm) -TTC was added to 15 ml of dioxane, and 0.155 g of tributyltin hydride and 0.00875 g of AIBN were added. The mixture was reacted at a temperature of 80 ° C for 15 hours, The combined TTC functionalities were removed.
One percent by weight of poly (tBAAm-co-NIPAAm) thus obtained was added to distilled water to prepare a composition for inhibiting gas hydrate formation.
Example 2 (tBAAm: NIPAAm = 5:15)
A composition for inhibiting gas hydrate formation was prepared in the same manner as in Example 1, except that 1.74 g and 4.66 g of tBAAm and NIPAAm were added, respectively.
Example 3 (tBAAm: NIPAAm = 1:19)
A composition for inhibiting the formation of gas hydrate was prepared in the same manner as in Example 1, except that 0.349 g and 5.90 g of tBAAm and NIPAAm were added, respectively.
Example 4
1% by weight of poly (tBAAm-co-NIPAAm) obtained according to Example 1 was added to an aqueous solution of 10% by weight of ethylene glycol to prepare a composition for inhibiting gas hydrate formation.
Example 5
1 wt% of poly (tBAAm-co-NIPAAm) obtained according to Example 2 was added to an aqueous 10 wt% ethylene glycol solution to prepare a composition for inhibiting gas hydrate formation.
Example 6
1 wt% of poly (tBAAm-co-NIPAAm) obtained according to Example 3 was added to an aqueous 10 wt% ethylene glycol solution to prepare a composition for inhibiting gas hydrate formation.
Comparative Example 1
Pure water was used to confirm the effect of the composition for inhibiting gas hydrate formation according to the present invention in inhibiting gas hydrate formation.
Comparative Example 2
1% by weight of PVCap [Poly (N-vinyl caprolactam)] was added to distilled water to prepare a composition for inhibiting gas hydrate formation.
Comparative Example 3
1% by weight of PVCap [Poly (N-vinyl caprolactam)] was added to a 10% by weight aqueous solution of ethylene glycol to prepare a composition for inhibiting gas hydrate formation.
Comparative Example 4 (tBAAm: NIPAAm = 1: 19)
27 ml of DMF was added to a reaction vessel equipped with a stirrer, a thermometer and a condenser. Then, 0.141 g and 2.38 g of tBAAm and NIPAAm, respectively, were added, and 0.124 g of AIBN was added. Free radical copolymerization to obtain poly (tBAAm-co-NIPAAm).
One percent by weight of poly (tBAAm-co-NIPAAm) thus obtained was added to distilled water to prepare a composition for inhibiting gas hydrate formation.
Comparative Example 5
1 wt% of poly (tBAAm-co-NIPAAm) obtained according to Comparative Example 4 was added to an aqueous 10 wt% ethylene glycol solution to prepare a composition for inhibiting gas hydrate formation.
<Test Example>
One H-NMR analysis
1 H-NMR analysis was performed to confirm the proportion of the monomers constituting the copolymer synthesized according to Examples 1 to 3. The results are shown in FIG.
Referring to FIG. 2, 1 H-NMR analysis carried out from the example 1 (Fig. 2a), Example 2 (Fig. 2b) and Example 3, respectively the copolymer 9:16, 5:15 and 1 (Fig. 2c) : 19 tBAAm: NIPAAm ratio.
SEC analysis
The number average molecular weight, weight average molecular weight, and polydispersity index (PDI) of poly (tBAAm-co-NIPAAm) synthesized according to the examples and comparative examples according to the present invention were calculated.
Fig. 3 shows the results of SEC analysis of the copolymer synthesized according to Example 2 (Fig. 3A) and 3 (Fig. 3B), and the results are summarized in Table 1 below.
(g / mol)
(g / mol)
Referring to Table 1, the polydispersity index (PDI) of poly (tBAAm-co-NIPAAm) synthesized according to Examples 2 and 3 was very low, 1.14 and 1.25, respectively, It was confirmed that a copolymer having a distribution was synthesized.
FIG. 4 also shows the results of SEC analysis of the copolymers synthesized according to Example 3 and Comparative Example 4, and the results are summarized in Table 2 below.
(g / mol)
(g / mol)
Referring to Table 2 above, the polydispersity index of the copolymer according to Comparative Example 4 is 2.3, whereas the polydispersity index of the copolymer according to Example 3 is 1.4, while the polydispersity index of the copolymer according to Comparative Example 4 is 2.3. It was confirmed that the coalescence had a relatively uniform molecular weight distribution as compared with the copolymer of Comparative Example 4. [
It is expected that the copolymers of Examples 1 to 6 have a constant physical property as compared with the copolymer of Comparative Example 4 because the molecular weight distribution of the copolymer is uniform as the polydispersity index is lower.
UV-visible light analysis
UV-visible light analysis was performed to evaluate the LCST and LCST sensitivities of the examples and comparative examples prepared according to the present invention.
5 is a photograph of the phase change in LCST for the composition for inhibiting gas hydrate production produced according to one embodiment of the present invention. Referring to FIG. 5, the composition for inhibiting the formation of gas hydrate according to the present invention is present as a transparent solution by dissolving in water at a temperature below the LCST, but it is present in a solid state at a temperature above the LCST to be changed into a cloudy solution.
6 shows UV-Visible analysis results of the composition for inhibiting the formation of gas hydrate produced in Examples 1 to 6, and the results are summarized in Table 3.
(° C)
Referring to Table 3, it was confirmed that the LCST increases as the proportion of the tBAAm monomer increases, and it is confirmed that the LCST is lowered when the aqueous 10 wt% ethylene glycol solution is used together.
FIG. 7 shows UV-Visible analysis results of the compositions for inhibiting gas hydrate formation according to Example 6 and Comparative Example 4, and the results are summarized in Table 4.
(° C)
(% / C)
The LCST sensitivity can be used as a measure of the change in the transmittance in the temperature range at which the phase change occurs and to compare the temperature response characteristics.
Referring to Table 4 above, the LCST of Example 6 and Comparative Example 5 are the same at 22.0 ° C, while the LCST sensitivity of Example 6 is 39% / ° C, while the LCST sensitivity of Comparative Example 5 is 24% / ° C Points can be confirmed. These results are due to the difference in PDI of the copolymer contained in the composition for inhibiting gas hydrate formation, and the temperature responsive function of the composition of Example 6 including the copolymer improved in PDI by the RAFT copolymerization method is improved, so that the LSCT sensitivity Can be understood as being improved.
Gas hydrate inhibition performance evaluation
The gas hydrate formation inhibiting performance of the examples and comparative examples prepared according to the present invention was evaluated. A high pressure autoclave reaction system was used. The gas hydrate conversion was measured under a temperature of 20 ° C to 2 ° C under a pressure of 100 atm, while the gas hydrate conversion was measured five times for each composition.
8 is a schematic diagram of a high pressure autoclave reaction system used for gas hydrate inhibition performance evaluation.
FIG. 9 shows the results of evaluating methane hydrate formation inhibition performance of the compositions for inhibiting gas hydrate production produced according to Examples 1 to 6 and Comparative Examples 1 to 3, and the results are summarized in Table 5.
Referring to Table 5, it can be confirmed that the compositions according to Examples 1 to 6 exhibit excellent gas hydrate inhibition performance as compared with Comparative Example 1 using pure water, and the comparative example including PVCap used as a conventional inhibitor It can be confirmed that it has similar gas hydrate suppression performance as compared with Examples 2 and 3.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that various modifications and changes may be made without departing from the scope of the present invention.
Claims (11)
a thermosensitive copolymer having a monomer ratio of t-butyl acrylamide (tBAAm) and N-isopropylacrylamide (NIPAAm) of 1: 1.5 to 19 and a polydispersity index (PDI) of 1.1 to 1.8; And
[Chemical Formula 1]
(Wherein n is an integer of 12 to 133 and m is an integer of 255 to 266)
menstruum; Wherein the composition is a composition for inhibiting gas hydrate formation,
Wherein the composition contains 0.1 to 3.0 wt% of the thermosensitive copolymer in the solvent and the lower critical solution temperature (LCST) is 10 to 28 DEG C.
Wherein the solvent is selected from the group consisting of distilled water, C 4 to C 6 alcohols, C 4 to C 6 glycols, C 4 to C 10 ethers, C 3 to C 10 esters, C 3 to C 10 ketones, Wherein the composition is any one selected from the group consisting of water,
The solvent is an aqueous solution of ethylene glycol,
Wherein the concentration of the aqueous ethylene glycol solution is in the range of 0.1 to 30% by weight.
Wherein the lower limit critical solution temperature of the composition is in the range of 4 to 23 占 폚.
(2) the chain transfer agent bound to the terminal of the polymerized polymer was removed and the monomer ratio of t-butyl acrylamide: poly (tBAAm-co-NIPAAm) was adjusted to 1: 1.5 to 19 to synthesize a block copolymer step; And
(3) mixing the synthesized copolymer with a solvent.
Wherein the t-butyl acrylamide (tBAAm) and the N-isopropylacrylamide (NIPAAm) are mixed at a weight ratio of 1: 1.5 to 20.
Wherein the solvent is selected from the group consisting of distilled water, C 4 to C 6 alcohols, C 4 to C 6 glycols, C 4 to C 10 ethers, C 3 to C 10 esters, C 3 to C 10 ketones, Lt; RTI ID = 0.0 > 1, < / RTI >
The solvent is an aqueous solution of ethylene glycol,
Wherein the concentration of the aqueous ethylene glycol solution is in the range of 0.1 to 30% by weight.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020170064128A KR101956354B1 (en) | 2017-05-24 | 2017-05-24 | A gas hydrate inhibitor having temperature-sensible and manufacturing method thereof |
| PCT/KR2018/005850 WO2018217013A2 (en) | 2017-05-24 | 2018-05-23 | Temperature-sensitive gas hydrate inhibitor and preparation method therefor |
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| KR101956354B1 true KR101956354B1 (en) | 2019-06-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150119299A1 (en) * | 2008-10-17 | 2015-04-30 | Ecolab Usa Inc. | Method of controlling gas hydrates in fluid systems |
| KR101647187B1 (en) | 2014-07-17 | 2016-08-10 | 단국대학교 천안캠퍼스 산학협력단 | Novel temperature responsive and cationic copolymer and use thereof |
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| US7981688B2 (en) * | 2007-03-08 | 2011-07-19 | University Of Washington | Stimuli-responsive magnetic nanoparticles and related methods |
| KR101188360B1 (en) | 2010-06-28 | 2012-10-05 | 한국에너지기술연구원 | A gas hydrate inhibitors and a method of inhibiting gas hydrate formation |
| KR101199547B1 (en) | 2010-10-04 | 2012-11-12 | 한국에너지기술연구원 | Gas hydrate inhibitors and a method of inhibiting gas hydrate formation |
| KR102082997B1 (en) * | 2012-03-19 | 2020-02-28 | 삼성전자주식회사 | Thermosensitive copolymers and forward osmosis water treatment devices and methods using the same |
| AU2013271364B2 (en) * | 2012-06-07 | 2017-03-02 | The University Of Queensland | Release media |
| KR20160065163A (en) * | 2013-10-02 | 2016-06-08 | 더루브리졸코오퍼레이션 | Amidoamine gas hydrate inhibitors |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150119299A1 (en) * | 2008-10-17 | 2015-04-30 | Ecolab Usa Inc. | Method of controlling gas hydrates in fluid systems |
| KR101647187B1 (en) | 2014-07-17 | 2016-08-10 | 단국대학교 천안캠퍼스 산학협력단 | Novel temperature responsive and cationic copolymer and use thereof |
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| J. Polym. Sci. Part A; Polym. Chem., Vol.44, Issue 21, 6410-6418(2006) |
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| WO2018217013A2 (en) | 2018-11-29 |
| WO2018217013A3 (en) | 2019-04-11 |
| KR20180128696A (en) | 2018-12-04 |
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