CN105090747B - A kind of Compositional type hydrate polymerization inhibitor containing rhamnolipid - Google Patents
A kind of Compositional type hydrate polymerization inhibitor containing rhamnolipid Download PDFInfo
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- CN105090747B CN105090747B CN201510501005.7A CN201510501005A CN105090747B CN 105090747 B CN105090747 B CN 105090747B CN 201510501005 A CN201510501005 A CN 201510501005A CN 105090747 B CN105090747 B CN 105090747B
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Abstract
A kind of Compositional type hydrate polymerization inhibitor containing rhamnolipid disclosed by the invention, it includes rhamnolipid biological surface activator and polyol-based non-ionic surfactant, and the mass ratio of rhamnolipid biological surface activator and polyol-based non-ionic surfactant is 0.01 100：1.In Compositional type hydrate polymerization inhibitor under rhamnolipid biological surface activator and polyol-based non-ionic surfactant effect, emulsion occurs for oil, aqueous phase, and aqueous phase is scattered in oil phase with small form of moisture drops, forms uniform water-in-oil type emulsion；With the formation of hydrate shell, hydrophilic radical in rhamnolipid biological surface activator molecule is easily adsorbed in shell layer surface, change the hydrophily of shell, make to assemble between shell and between shell and water droplet, hydrate particle is set to be dispersed in oil phase without building up, so as to play the purpose for preventing gas hydrate from assembling deposition, have the advantages that consumption is small, economic and environment-friendly, polymerization inhibition performance is excellent.
Description
Technical Field
The invention relates to the technical field of oil and gas transmission, in particular to a rhamnolipid-containing compound type hydrate polymerization inhibitor.
Background
The gas hydrate is formed by gas molecules (CH)4、C2H6、CO2And H2S, etc.) form non-stoichiometric crystalline cage-like substances with water molecules under low temperature and high pressure conditions, often referred to as combustible ice. The most common hydrate structures at present are of three types: form I, form II and form H. The hydrate technology is widely applied to the fields of environmental protection, oil-gas mixed transportation, gas separation, air-conditioning cold accumulation, biological pharmacy and the like. However, despite the remarkable research results in the last decades for hydrate technology, the flow safety problems caused by gas hydrate plugging have long plagued the oil and gas production and transportation sector, especially for oil-gas-water multiphase transport systems, where hydrate problems are more severe.
The traditional thermodynamic inhibition method changes the thermodynamic formation conditions of system hydrates by mainly removing a water phase, heating a pipeline, reducing pressure, adding a hydrate thermodynamic inhibitor and the like, so that no hydrate is formed in the process of pipeline transportation. The dehydration technology is a method commonly used in the prior natural gas pipeline transportation for removing a water phase in a system so as to prevent the formation of hydrates. However, the method is difficult to completely remove the water phase in the pipeline, and the water phase possibly exists in the local part, so that the method still has a great blocking risk. The heating pipeline method is to increase the temperature of the system to be higher than the corresponding hydrate generation temperature under the pressure of the system, so that the blockage caused by the formation of the hydrate is avoided. The depressurization method is to reduce the pressure of the pipeline to be lower than the corresponding hydrate generation pressure at the system temperature, thereby avoiding the generation of the hydrate. However, this method is very limited in its use since the pipeline delivery pressure cannot be changed at will in general. Adding a hydrate thermodynamic inhibitor, such as methanol, ethylene glycol, etc., changes the thermodynamic equilibrium conditions of the system hydrates, such as the formation pressure is higher than the pipeline transportation pressure or the formation temperature is lower than the pipeline transportation temperature, thereby avoiding the formation of hydrates in the pipeline. However, the method has the disadvantages of large dosage of the inhibitor, usually 30 to 50 percent of the water content of the system, high cost, easy pollution to the environment and the like.
Over the last twenty years, significant advances have been made in hydrate low dose inhibitors as an alternative to traditional thermodynamic inhibition methods. The low-dose inhibitor comprises two types of hydrate kinetic inhibitors and hydrate inhibitors. The hydrate kinetic inhibitor is generally some water-soluble high molecular polymers, which do not change the thermodynamic equilibrium condition of the system hydrate, but are adsorbed on the surface of hydrate particles, thereby preventing or delaying the further growth of hydrate crystal grains, ensuring that no blockage occurs in the conveying process, but the inhibition performance of the hydrate kinetic inhibitor is often influenced by the supercooling degree of the system. Hydrate polymerization inhibitors are polymers and surfactants which can only be used in the presence of both oil and water phases. The hydrate inhibitor does not change the generation condition of the hydrate, allows the formation of the hydrate in the system, but can control the size of hydrate particles, prevent the aggregation and deposition of the hydrate particles and finally enable the hydrate particles to be transported in stable slurry. From the sustainable maximum supercooling degree and the practical application field (oil-gas-water multiphase mixed transportation system), the gas hydrate polymerization inhibitor is the only choice.
In the aspect of development of hydrate polymerization inhibitor, the hydrate polymerization inhibitor is obtained by compounding polyoxyethylene dicarboxylate gemini nonionic surfactant and polyol type nonionic surfactant in the prior art, and has the defects of large addition amount of the polymerization inhibitor, viscous hydrate slurry formed under the condition of high water content and large pipe transmission pressure resistance.
Yet another way is: the mixture of the kinetic inhibitor, nitrate and acetate is injected into produced or transported oil-gas fluid to play the role of inhibiting hydrate blockage, but the inhibitor only can start the mechanical inhibiting effect and has small bearable supercooling degree, when the hydrate is formed in the system, the inhibiting effect is lost, and the application range is severely limited.
Accordingly, the prior art is subject to further improvement and development.
Disclosure of Invention
In view of the defects of the prior art, the invention provides the rhamnolipid-containing compound type hydrate polymerization inhibitor, which is used for improving the polymerization inhibition performance and reducing the addition amount of the rhamnolipid-containing compound type hydrate polymerization inhibitor.
In order to solve the technical problem, the scheme of the invention comprises the following steps:
a compound type hydrate polymerization inhibitor containing rhamnolipid comprises rhamnolipid biosurfactant and polyhydric alcohol type nonionic surfactant, wherein the mass ratio of the rhamnolipid biosurfactant to the polyhydric alcohol type nonionic surfactant is 0.01-100: 1.
the mass ratio of the rhamnolipid biosurfactant to the polyhydric alcohol type nonionic surfactant is 0.1-10: 1.
the compound hydrate polymerization inhibitor is characterized in that the rhamnolipid biosurfactant is biosurfactant generated by pseudomonas or burkholderia, and comprises two rhamnolipids RH1 and RH 2:
RH1 is:
RH2comprises the following steps:
the compound hydrate polymerization inhibitor comprises one or a mixture of span 20, span40, span60, span 65, span80 and span 85 as the polyhydric alcohol type nonionic surfactant.
The composite hydrate polymerization inhibitor has a lipophilic and hydrophilic value of 3-9.
The composite hydrate polymerization inhibitor comprises the following components in percentage by weight:
wAis the mass of rhamnolipid biosurfactant, wBQuality of polyol-type nonionic surfactant, HLBAWherein,
is the lipophilic value, HLB, of rhamnolipid biosurfactantBIs lipophilic and hydrophilic of polyhydric alcohol type nonionic surfactant.
The rhamnolipid-containing compound type hydrate polymerization inhibitor provided by the invention is not only dissolved in methanol, chloroform and ether, but also shows good dissolution characteristics in an alkaline aqueous solution, has good chemical and biological characteristics, and has oil and water amphipathy; the rhamnolipid biosurfactant can be used under extreme conditions of temperature, pH value and salinity, is nontoxic, can be quickly biodegraded, and avoids pollution to the environment; the polyhydric alcohol type nonionic surfactant has good emulsifying property, and can form uniform and stable water-in-oil emulsion; the rhamnolipid biosurfactant has good oil and water amphipathy, and the hydrophilic group and the lipophilic group in the structure enable the rhamnolipid biosurfactant to be easily adsorbed on an oil-water interface, so that the rhamnolipid biosurfactant and the lipophilic group are compounded to easily form uniform and stable water-in-oil type emulsion. Before the hydrate is formed, under the action of a rhamnolipid biosurfactant and a polyol type nonionic surfactant in the compound type hydrate polymerization inhibitor, an oil phase and a water phase are emulsified, and the water phase is dispersed in an oil phase in a form of small water drops to form a uniform water-in-oil type emulsion; along with the formation of a hydrate shell layer, hydrophilic groups in rhamnolipid biosurfactant molecules are easily adsorbed on the surface of the shell layer, the hydrophilicity of the shell layer is changed, aggregation among the shell layers and between the shell layer and water drops is avoided, lipophilic long-chain groups extend into an oil phase, hydrate particles are uniformly dispersed in the oil phase and are not accumulated, and the purpose of preventing gas hydrate from being aggregated and deposited is achieved. The amount of water in the system is generally controlled to be 0.1-10%, preferably 0.5-3%, and in the concentration range, the polymerization inhibition effect can be improved by increasing the addition amount of the polymerization inhibitor.
Drawings
FIG. 1 is a schematic structural view of a high-pressure sapphire reaction kettle;
FIG. 2 is a schematic view of a high pressure sapphire reaction vessel with a measuring probe;
wherein, 1-a high-pressure sapphire reaction kettle body; 2-constant temperature air bath; 3-a temperature sensor; 4-a pressure sensor; 5-hand pump; 6-automatic data acquisition system; 7-a piston; 8-a stirrer; 9-PVM probe; 10-FBRM probe; 11-high pressure autoclave; 12-a temperature data acquisition system; 13-pressure data acquisition system.
Detailed Description
The invention provides a compound type hydrate polymerization inhibitor containing rhamnolipid, and the invention is further detailed in the following in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a rhamnolipid-containing compound type hydrate polymerization inhibitor, which comprises a rhamnolipid biosurfactant and a polyol type nonionic surfactant, wherein the mass ratio of the rhamnolipid biosurfactant to the polyol type nonionic surfactant is 0.01-100: 1. furthermore, the mass ratio of the rhamnolipid biosurfactant to the polyhydric alcohol type nonionic surfactant is 0.1-10: 1.
in another preferred embodiment of the present invention, the rhamnolipid biosurfactant is produced by pseudomonas or burkholderia, and comprises two rhamnolipids of RH1 and RH 2:
RH1 is:
RH2 is:
the polyhydric alcohol type nonionic surfactant is one or mixture of span 20, span40, span60, span 65, span80 and span 85.
And the oleophylic and hydrophilic value of the compound hydrate polymerization inhibitor is 3-9.
The composite hydrate polymerization inhibitor comprises the following components in percentage by weight:
wAis the mass of rhamnolipid biosurfactant, wBQuality of polyol-type nonionic surfactant, HLBAWherein,
is the lipophilic value, HLB, of rhamnolipid biosurfactantBIs lipophilic and hydrophilic of polyhydric alcohol type nonionic surfactant.
To further illustrate the present invention, the following examples are given by way of illustration and not limitation.
Example 1
The compound hydrate polymerization inhibitor is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span80 in a weight ratio of 1: 1 in a mass ratio of 1.
The above-mentioned composite hydrate polymerization inhibitor was applied to an oil-water system having a water content of 10% (calculated based on the sum of the volumes of water and oil), and the effect of the composite hydrate polymerization inhibitor of this example was evaluated.
A high-pressure sapphire reaction kettle is adopted for system evaluation, and the structural schematic diagram is shown in figure 1. The device mainly comprises a high-pressure sapphire reaction kettle body 1, a constant-temperature air bath 2, a temperature sensor 3, a pressure sensor 4, a hand-push pump 5, a stirring system and a computer data automatic acquisition system 6. The maximum working volume of the high-pressure sapphire reaction kettle is 49cm3The highest working pressure is 50MPa, and the working temperature range is 183K-423K. A closed piston 7 is arranged in the reaction kettle, pressurized fluid (petroleum ether) can be separated from an experimental system, and the pressure in the reaction kettle can be adjusted through a hand-push pump 5. In addition, an LGY150A type cold light source is arranged outside the sapphire reaction kettle.
The specific steps of the application evaluation experiment carried out by adopting the high-pressure sapphire reaction kettle are as follows:
(1) after the whole experiment system is cleaned, preparing an oil-water emulsion containing the compound type hydrate polymerization inhibitor of the embodiment, wherein 15mL of the oil-water emulsion is placed in a high-pressure sapphire reaction kettle body 1, and the system temperature is set to be 274.2K, namely the experiment temperature;
(2) when the temperature in the high-pressure sapphire reaction kettle body 1 reaches a preset value and is stable for 4 hours, vacuumizing the system, introducing experimental gas for replacement for 3 times, wherein the composition of simulated natural gas used for the experiment is shown in table 1, and continuously introducing a certain amount of experimental gas to enable the experimental gas to reach dissolution balance, namely the amount of injected gas enables the gas pressure during balance to be smaller than the corresponding hydrate balance pressure at the temperature;
(3) introducing experimental gas until the system pressure is 7.2MPa, namely the experimental pressure, closing the air inlet valve, opening the stirrer, and keeping the stirring speed constant in the whole experimental process; along with the reaction, the gas is continuously consumed, in order to keep the initial pressure of the system, the hand-push pump 5 is pushed to change the volume of the reaction system so as to keep the volume constant, 5 degrees of the hand-push pump are recorded to calculate the gas consumption volume, meanwhile, the macroscopic morphological change of the gas hydrate in the system is observed, and the temperature, the pressure and the reaction time of the system are all recorded by the automatic computer data acquisition system 6;
(4) when the system pressure is constant and kept for 4 hours, the reaction of the gas hydrate is considered to be terminated, the upper layer gas is taken for chromatographic analysis, the actual supercooling degree is calculated according to the gas composition, and the supercooling degree is the difference between the equilibrium temperature (the equilibrium temperature is calculated by a Chen-Guo model) of the gas hydrate and the experimental temperature under the same experimental pressure;
(5) the temperature of the system is adjusted to 303K, and after the gas hydrate in the reaction kettle is completely decomposed, the next group of experiments are restarted.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), and the addition amount of the polymerization inhibitor in this example is 1.0% of the water content in the system.
TABLE 1
The experimental phenomena that the hydrate polymerization inhibitor can effectively prevent gas hydrate from accumulating and agglomerating are as follows: under the conditions of experiment temperature and pressure, hydrate particles formed in the experiment process are uniformly dispersed in the oil phase, the system is in slurry distribution, the phenomenon of hydrate accumulation and agglomeration is avoided, and a stirrer in the reaction kettle can stably and freely stir up and down.
In the whole experimental process of the embodiment, gas hydrate particles are uniformly dispersed in the oil phase, the phenomenon of hydrate accumulation, agglomeration and blockage does not occur after continuous operation for 12 hours, and a stirrer in the reaction kettle can freely move up and down; after stirring is stopped, the gas hydrate can be found to be gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the lower layer is a hydrate phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, hydrate particles are re-dispersed, and the phenomenon of agglomeration is still avoided, so that the polymerization inhibitor provided by the embodiment has good polymerization inhibition performance.
Example 2
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span80 in a weight ratio of 0.25: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 3
The complex hydrate polymerization inhibitor in the embodiment is prepared by mixing rhamnolipid biosurfactant and polyhydric alcohol type nonionic surfactant Span80 in a weight ratio of 0.5: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 4
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span80 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 5
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span in a weight ratio of 4: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 6
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span80 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 3.0ml of deionized water and 12ml of-20 # diesel oil, i.e. the oil-water system with a water content of 20% (calculated by taking the sum of the volumes of water and oil as a reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 7
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span80 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 4.5ml of deionized water and 10.5ml of-20 # diesel oil, i.e. the oil-water system with a water content of 30% (calculated by taking the sum of the volumes of water and oil as a reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 8
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing a rhamnolipid biosurfactant and a polyol type nonionic surfactant Span80 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 6.0ml of deionized water and 9.0ml of-20 # diesel oil, i.e. the oil-water system with a water content of 40% (calculated by taking the sum of the volumes of water and oil as a reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 9
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span 20 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 10
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing a rhamnolipid biosurfactant and a polyol type nonionic surfactant Span40 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 11
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing a rhamnolipid biosurfactant and a polyol type nonionic surfactant Span60 in a ratio of 2: 1, in a mass ratio of 1.
In this example, the high-pressure sapphire reaction kettle described in example 1 was used for evaluation, and the specific experimental procedure was as described in example 1.
In this example, the oil-water system in the reaction kettle is composed of 1.5ml of deionized water and 13.5ml of-20 # diesel oil, i.e. the oil-water system with water content of 10% (calculated by taking the sum of the volumes of water and oil as the reference), the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system, and the composition of the introduced experimental gas is shown in table 1.
In the whole experimental process of the embodiment, hydrate particles are uniformly dispersed in an oil phase, the continuous operation for 12 hours does not cause the phenomenon of hydrate accumulation, agglomeration and blockage, and a stirrer of a reaction kettle can freely move up and down; after stirring is stopped, gas hydrate particles are gradually deposited at the bottom of the reaction kettle, the upper layer is an oil phase, the reaction kettle can be restarted smoothly after stirring is stopped for 12 hours, the hydrate particles are re-dispersed, and the phenomenon of agglomeration is avoided, so that the polymerization inhibitor provided by the embodiment also has good polymerization inhibition performance.
Example 12
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing a rhamnolipid biosurfactant and a polyol type nonionic surfactant Span80 in a ratio of 2: 1, in a mass ratio of 1.
The nonionic composite gas hydrate anti-agglomerant is applied to an oil-water system with the water content of 10 percent (calculated by taking the sum of the volumes of water and oil as a reference), and the form and the particle size distribution rule of the gas hydrate in the forming process are measured.
In order to examine the morphological change and the Particle size distribution rule in the formation process of the hydrate in the oil-water system in the presence of the compound hydrate polymerization inhibitor, the present embodiment is tested in an autoclave 11 equipped with an online Particle laser visualization analyzer (PVM) probe 9 and an online Focused Beam Reflectance Meter (FBRM) probe 10, and the structural schematic diagram is shown in fig. 2. The device mainly includes: an autoclave 11 with water bath and mechanical stirring, a PVM measuring probe 9/FBRM measuring probe 10 and related connecting devices and a data acquisition system. The autoclave 11 is made of stainless steel and can bear the maximum pressure of 32MPa, and the effective volume of the autoclave 11 is 534.72mL (the inner diameter is 51.84mm, and the height of the autoclave is 297.32 mm); the operating temperature range of the constant-temperature water bath is 253K-323K; the mechanical stirring is composed of a motor, an impeller in the autoclave and the like, so that the reaction system in the autoclave 11 is uniformly mixed.
Wherein the PVM measuring probe 9 consists of six beams of laser, the area in front of the probe (1680 μm x 1261 μm) is illuminated by the laser beams, and then the microscopic morphological change in the visible area is shot. The FBRM measuring probe 10 is also used for measuring by emitting laser light, which emits near infrared wavelengths to be transmitted to the probe end through an optical fiber, the probe end is provided with a rotating optical lens to deflect the light, the emitted laser light is reflected when being scanned on the surface of a particle in the experimental process, and the chord length is determined by the time from measurement to reflection and the scanning speed of the laser light. The laser scanning speed during the measurement process can be adjusted between 2 and 16m/s according to the experimental requirements. The number of chord lengths of the droplets or particles measured over a time interval through a sapphire window in front of the probe is statistically derived.
The specific steps of the experiment using the above autoclave were as follows:
(1) prior to the start of the experiment, the autoclave 11 and all the connected parts were flushed with a cleaning solution and blown dry with nitrogen. Wiping the PVM measuring probe 9 and the FBRM measuring probe 10 to ensure that the PVM measuring probe and the FBRM measuring probe are installed after the PVM measuring probe and the FBRM measuring probe meet the measurement requirement;
(2) injecting 220mL of an oil-water system prepared in advance and the hydrate polymerization inhibitor of the embodiment into the autoclave 11, and evacuating air dissolved in the solution by vacuumizing;
(3) starting the FBRM measuring probe 9, the PVM measuring probe 10, the temperature data acquisition system 12 and the pressure data acquisition system 13, adjusting the temperature to 274.2K in a water bath, starting cooling, starting stirring at the rotating speed of 1000r/min, and starting the data acquisition system;
(4) when the temperature in the high-pressure kettle 11 reaches the experimental temperature and is kept for 4 hours, stopping stirring, introducing gas until the experimental pressure is 8.0MPa, and observing the form change and the particle size distribution change rule of the gas hydrate formation process;
(5) when the hydrate in the high-pressure kettle 11 is formed stably, stopping stirring for 2 hours, restarting, and observing the influence of stirring stopping on hydrate slurry;
(6) and adjusting the temperature of the water bath to 303K, and after the hydrate is decomposed, exhausting and draining the gas and restarting the next set of experiments.
In this example, the oil-water system in the autoclave 11 was composed of 22ml of deionized water and 198ml of-20 # diesel, i.e., a mixed transportation system with a water content of 10% (calculated based on the sum of the volumes of water and oil), the addition amount of the anti-agglomerant in this example was 1.0% of the mass of water in the system, the gas phase used was simulated natural gas, and the gas composition was as shown in table 1 in example 1.
In the experimental process of this example, as the gas hydrate is formed in the system, the uniform hydrate slurry is finally formed by the pictures taken by the PVM when the gas hydrate is completely generated. According to the change condition of the chord length distribution of hydrate slurry particles measured by FBRM, along with the formation of hydrates, the particle size of the gas hydrate in the system shifts to the size of large particles, but along with the experiment, the particle size of the gas hydrate tends to be stable, after the stirring is stopped, due to the density difference between a hydrate phase and an oil phase, the sedimentation phenomenon of the hydrate particles occurs, but after the stirring is restarted, the hydrate particles can be uniformly dispersed again, and the blocking and caking phenomenon (the wall sticking of the gas hydrate does not occur on two probes) does not occur, so that the polymerization inhibitor of the embodiment has good polymerization inhibition performance.
Example 13
The complex hydrate polymerization inhibitor of the embodiment is prepared by mixing rhamnolipid biosurfactant and polyalcohol nonionic surfactant span80 in a ratio of 2: 1, in a mass ratio of 1.
This example uses the experiment carried out in the autoclave 11 of example 12, the specific experimental procedure being as described in example 12.
In this example, the oil-water system in the reaction kettle is composed of 44ml of deionized water and 176ml of-20 # diesel oil, i.e. the oil-water system with a water content of 20% (calculated by taking the sum of the volumes of water and oil as a reference), and the addition amount of the polymerization inhibitor in this example is 1.0% of the mass of water in the system.
In the whole experiment process of the embodiment, along with the formation of gas hydrate in the system, the deviation of the particle size of the gas hydrate in the system to the large particle size can be found in the FBRM, but as the experiment progresses, the particle size of the gas hydrate tends to be stable, and after the stirring is stopped for 2h and the system is restarted, the block wall sticking phenomenon (no wall sticking of the gas hydrate occurs on both probes) does not occur, so that the polymerization inhibitor of the embodiment has good polymerization inhibition performance.
It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A compound type hydrate polymerization inhibitor containing rhamnolipid comprises rhamnolipid biosurfactant and polyhydric alcohol type nonionic surfactant, wherein the mass ratio of the rhamnolipid biosurfactant to the polyhydric alcohol type nonionic surfactant is 0.01-100: 1;
the oleophylic hydrophilic value of the compound hydrate polymerization inhibitor is 3-9;
the oleophylic and hydrophilic values are as follows:
wAis the mass of rhamnolipid biosurfactant, wBQuality of polyol-type nonionic surfactant, HLBAWherein,
is the lipophilic value, HLB, of rhamnolipid biosurfactantBIs the oleophilic hydrophilic value of the polyhydric alcohol type nonionic surfactant; the compound hydrate polymerization inhibitor is used for an oil-gas-water three-phase mixed transportation system with the water volume not more than 60 percent of the total volume of oil and water.
2. The composite hydrate polymerization inhibitor as claimed in claim 1, wherein the mass ratio of the rhamnolipid biosurfactant to the polyol-type nonionic surfactant is 0.1-10: 1.
3. the composite hydrate inhibitor according to claim 1, wherein the rhamnolipid biosurfactant is a biosurfactant derived from pseudomonas or burkholderia, and comprises two rhamnolipids of RH1 and RH 2:
RH1 is:
RH2 is:
4. the compound type hydrate polymerization inhibitor according to claim 1, wherein the polyol-type nonionic surfactant is one or a mixture of span 20, span40, span60, span 65, span80 and span 85.
5. The compound hydrate polymerization inhibitor according to claim 1, wherein the amount of the compound hydrate added is 0.1-10% of the water content of the system.
6. The compound hydrate polymerization inhibitor according to claim 5, wherein the amount of the compound hydrate added is 0.5 to 3.0% of the amount of water in the system.
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