CN114716972A - Oil gas inhibitor composition and method for inhibiting volatilization of liquid organic hydrocarbon - Google Patents
Oil gas inhibitor composition and method for inhibiting volatilization of liquid organic hydrocarbon Download PDFInfo
- Publication number
- CN114716972A CN114716972A CN202011534774.4A CN202011534774A CN114716972A CN 114716972 A CN114716972 A CN 114716972A CN 202011534774 A CN202011534774 A CN 202011534774A CN 114716972 A CN114716972 A CN 114716972A
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- composition
- weight
- organic hydrocarbon
- sodium
- water
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
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Abstract
The invention provides an oil gas inhibitor composition and a method for inhibiting volatilization of liquid organic hydrocarbon, the composition comprises a film forming agent, an emulsifier, a tension reducing agent and a solvent, and the hydrophilic-lipophilic balance value of the composition is 15-20. The composition of the present invention can achieve the object of reducing the amount of the surfactant and suppressing the volatilization of the organic hydrocarbon liquid for a long period of time. The dosage of the oil gas inhibitor composition provided by the invention is 10-100g relative to the surface dosage of the organic hydrocarbon liquid stored per square meter, and after the oil gas inhibitor composition is used for 24 hours, the content of the organic hydrocarbon liquid above the surface of the organic hydrocarbon liquid is still lower than 100% LEL.
Description
Technical Field
The present invention relates to an oil and gas inhibitor composition and a method for inhibiting volatilization of liquid organic hydrocarbons by using the oil and gas inhibitor composition.
Background
In the transportation and storage processes of volatile hydrocarbon organic matters, a large amount of harmful gases such as VOC and the like are generated, so that on one hand, the waste of resources is caused, and on the other hand, the pollution to the environment is also caused. In addition, in the process of checking and cleaning the storage and transportation equipment of hydrocarbon organic matters, volatile VOC and other harmful gases bring great harm to workers and have the risk of burning and explosion. At present, the method of introducing external air or replacing with nitrogen to discharge organic volatile matters in a limited space is commonly adopted in the industry, and the burning explosion accident caused by the contact of the organic volatile matters and oxygen in the air is avoided. However, the method needs a long time and is low in efficiency, the problem of residual oil volatilization cannot be fundamentally solved, and great safety uncertainty exists.
Currently, surfactants, solid floats, and combinations thereof have been coated onto the surface of liquids to reduce the evaporation rate of the liquid. For example, surfactants or solid floats have been added to the surface of water to reduce evaporation of water. Although the solid floating objects can seal the surface of the liquid and reduce the volatilization of the liquid, gaps exist among the solid floating objects, and the sealing effect is not ideal. Most preferably, the liquid seal is performed by using a surfactant, and a seamless and dead-corner-free seal can be realized. Because the surface tension of water is high, the surface tension of the surfactant is relatively low, the surfactant can be easily and rapidly spread on the surface of the water, the water surface is horizontally sealed by a molecular film, and the evaporation of the water is reduced. However, this method is not suitable for liquid hydrocarbon organic compounds because the surface tension ratio of liquid hydrocarbon organic compounds is low, and the surface tension of common surfactants is relatively high, and such surfactants are difficult to form a diffused sealing film on the surface of liquid hydrocarbon organic compounds quickly, and thus it is difficult to achieve a full sealing effect. In order to reduce the surfactant surface tension, CN108136360A discloses a method for placing a surfactant on a bulk liquid to reduce evaporation of the bulk liquid, the method comprising: providing a spray liquid surfactant composition having nano-sized droplets; generating a stream of aerosolized liquid surfactant composition through an atomizing nozzle to deposit the aerosolized liquid surfactant composition onto a surface of the bulk liquid to form a self-assembled layer thereon to reduce evaporation of the bulk liquid, wherein the liquid surfactant composition has a bulk density that is greater than a bulk density of the bulk liquid; and reducing the evaporation rate of the bulk liquid. Wherein the nano-sized droplets range from one micelle to 1000nm, causing the liquid surfactant composition to flow. The surfactant composition consists essentially of: a nonionic surfactant having an optionally branched C8 to C100 carbon chain, water at a concentration of about 1% w/v to about 50% w/v, and a polyglycol, preferably polyethylene glycol, wherein the polyglycol is present in a ratio of 10:1 by weight to 1:10 by weight relative to the total weight of the surfactant, and wherein the average droplet size is in the range of a single micelle to 1000 nm. The nonionic surfactant has a hydrophilic-lipophilic balance of greater than 10. The method prevents the liquid from evaporating by forming a nonionic surfactant into an aerosol film layer and laying the aerosol film layer on the surface of the liquid to form an insulating layer with air on the surface of the liquid. According to the description of the examples of this document, in a preferable environment in which 50 liters of commercially available gasoline can be charged into a 75000 liter can having a diameter of 0.3 meter and a length of 12 meters to generate fuel vapor and the environment around the can is clean and free from the influence of foreign matter, etc., the method achieves an LEL (lower explosion limit) of 0 for about 48 hours and an LEL of 25 for 48 hours under a humidity of 98% RH at a temperature and a humidity of 20.5 ℃ and 60% RH (relative humidity), respectively, in the can. Obviously, the method has great influence on the environment, particularly the humidity, and the effect of preventing the evaporation of oil gas in the practical application environment can be expected to be worse.
Disclosure of Invention
The invention aims to provide a green oil gas inhibitor composition and a liquid organic hydrocarbon volatilization inhibition technology which have better oil gas volatilization inhibition effect, no pollution to the environment and no toxicity to human bodies, and can inhibit the volatilization of organic hydrocarbon liquid for a long time by using a smaller amount of the composition.
The inventor of the present invention, in the course of studying the technology disclosed in CN108136360A, found that when the method of the technology is applied to a tank with a diameter of 3 meters and a volume of 30 cubic meters in a gas station, the initial hours (lower explosion limit) is 0% LEL, and after 14 hours, the LEL rapidly increases to 90% or more. The inventor of the invention discovers through further research that the inhibition effect can be effectively improved, the application range can be enlarged, and the requirement on the environment can be reduced by further adding the emulsifier and the tension reducing agent and controlling the hydrophilic-lipophilic balance value of the system to be 10-25.
The invention provides an oil gas inhibitor composition, which comprises a film-forming agent, an emulsifier, a tension-reducing agent and a solvent, wherein the hydrophilic-lipophilic balance value of the composition is 10-25, preferably 15-20.
In a second aspect, the present invention provides a method of inhibiting the evaporation of liquid organic hydrocarbons, which comprises atomising an oil and gas inhibitor composition as hereinbefore described to form particles having a particle size of from 1nm to 100 μm, preferably from 500nm to 50 μm, and then allowing the particles to settle or pass onto the surface of the organic hydrocarbon liquid.
The invention can achieve the purpose of inhibiting the volatilization of the organic hydrocarbon liquid for a long time in a poor environment close to the practical application environment and can reduce the dosage of an inhibitor composition, particularly a surfactant by compounding a film forming agent, an emulsifier, a tension reducing agent and a solvent to obtain a composition with the hydrophile-lipophile balance value of 10-25, preferably 15-20, atomizing the composition into particles with the particle size of 1nm-100 mu m, preferably 500nm-50 mu m, and then depositing or delivering the particles to the surface of the organic hydrocarbon liquid. The dosage of the oil gas inhibitor composition provided by the invention is 10-100g relative to the surface dosage of the organic hydrocarbon liquid stored per square meter, and after the oil gas inhibitor composition is used in an environment of 50 ℃ and 90% RH for 20 hours, the content of the organic hydrocarbon liquid above the surface of the organic hydrocarbon liquid is still maintained at about 0% LEL, and only reaches about 10% LEL after 120 hours. Whereas the blank without the addition of the inhibitor composition rapidly reached 45% LEL at 10 hours
Drawings
FIG. 1 is a graph showing the change of VOC concentration within 120 hours in test example 1 and test example 13 of the present invention;
FIG. 2 is a graph showing the change in VOC concentration within 2 hours in test example 13;
fig. 3 is a graph showing the change in VOC concentration of test example 14.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides an oil and gas inhibitor composition comprising a film-forming agent, an emulsifier, a tonicity-reducing agent and a solvent, the composition having a Hydrophilic Lipophilic Balance (HLB) of from 10 to 25, preferably from 15 to 20.
The invention enables the film forming agent, the emulsifier, the tension reducer and the solvent to act in a matching way, controls the hydrophile-lipophile balance value (HLB value) to be 10-25, preferably 15-20, can achieve the aim of inhibiting the volatilization of organic hydrocarbon liquid for a long time in a poor environment close to the practical application environment, and can reduce the dosage of the inhibitor composition, particularly the surfactant.
Preferably, the film-forming agent is present in an amount of 10 to 90 wt%, preferably 50 to 90 wt%, based on the total amount of the composition; the content of emulsifier is 1-10 wt%, preferably 2-5 wt%; the content of the tension reducer is 1-10 wt%, preferably 1-5 wt%; the content of the solvent is 1 to 70% by weight, preferably 5 to 20% by weight.
According to the composition, the film forming agent is used for enabling the composition to form a covering film on the surface of the liquid organic hydrocarbon. Preferably, the film former is a polyglycol and/or a fatty acid ethylene oxide adduct. According to a preferred embodiment of the invention, the film-forming agent is a polyethylene glycol and/or a fatty acid ethylene oxide adduct.
In the present invention, the number average molecular weight of polyethylene glycol is preferably in the range of 100-10000, more preferably PEG-4000, PEG-6000 or PEG-8000, and still more preferably PEG-4000.
In one embodiment, the fatty acid ethylene oxide adduct has an HLB of from 11 to 15.
In the preferred embodiment described above, the cover film is easy to form, is not easily broken, or is rapidly self-healing even if broken.
The HLB value may measure the magnitude and strength balance between hydrophilic and lipophilic groups in a surfactant molecule. When the HLB of the fatty acid ethylene oxide addition product is 11-15, the fatty acid ethylene oxide addition product can be well dissolved with water and oil, and has good emulsifying capacity so as to improve the attachment of the safety protection composition of oil and gas equipment on the surface of an oil body, and the composition can not fall off or settle.
In one embodiment, the fatty acid ethylene oxide adduct is selected from one or more of polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monolaurate; preferably, the fatty acid ethylene oxide adduct is selected from polyoxyethylene monolaurate; preferably, the number average molecular weight of the fatty acid ethylene oxide adduct is in the range of 1000-12000. More preferably, the polyoxyethylene monolaurate has an HLB of 13.1; the polyoxyethylene monolaurate is S-307.
In the present invention, the emulsifier acts as an emulsifier in the composition, and helps the composition to form a film. Preferably, the emulsifier is one or more of imidazoline and water-soluble salt thereof, polyacrylamide, hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose. Because the imidazole and the water-soluble salt thereof also have the effects of resisting static electricity, sterilizing and generating air bubbles, the emulsifier is preferably imidazoline and the water-soluble salt thereof.
In the present invention, the water-soluble salt refers to a salt which meets the general water-solubility requirement, such as one or more of potassium salt, sodium salt and ammonium salt.
In the invention, the imidazoline and the water-soluble salt thereof are nontoxic and easy to biodegrade, do not pollute the environment, and have the capability of sterilization and disinfection; the inhibitor is easy to have good compatibility with cationic compounds, anionic compounds and nonionic compounds, and can improve the uniformity of an inhibitor system; it also helps to increase the intermolecular forces of the inhibitor system, thereby increasing the stability of the oil surface water film.
In one embodiment, the imidazoline water-soluble salt can be prepared by a vacuum method or a solvent method using fatty acid and polyamine as raw materials, for example, the imidazoline water-soluble salt is imidazoline quaternary ammonium laurate salt, and the preparation method comprises the following steps: weighing a certain amount of lauric acid imidazoline intermediate, putting the lauric acid imidazoline intermediate into a three-neck flask, adding a proper amount of isopropanol solvent, heating and stirring to 60-100 ℃, preferably 80 ℃, dropwise adding a sodium chloroacetate solution with the mass fraction of 10-25%, preferably 16%, into the three-neck flask by using a dropping funnel in a manner that the molar ratio of the lauric acid imidazoline intermediate to the sodium chloroacetate is 1:1-3, preferably 1:2, adjusting the pH value of a reaction system to be 7.5-8.5 by using a sodium hydroxide solution in the reaction process, carrying out heat preservation reaction for 3-5 hours, preferably 4 hours, finally removing the isopropanol solvent from the reaction system by using a reduced pressure distillation method, pouring out the product when the product is hot, and cooling to obtain the lauric acid imidazoline quaternary ammonium salt. Other imidazoline quaternary ammonium salts can be prepared or commercially available with reference to the methods described above.
In the invention, the polyacrylamide is anionic polyacrylamide, the number average molecular weight of the polyacrylamide is preferably 50-200 ten thousand, and more preferably, the commercial brand (a propagation source) is one or more of commercial products such as a propagation source C620, a propagation source N300, a propagation source A-150Y and the like.
In the present invention, the tension reducing agent is used for reducing the tension of the composition, preferably, the tension reducing agent is one or more of amino acid and its water-soluble salt, phosphate ester, sodium dodecyl benzene sulfonate, potassium dodecyl benzene sulfonate, sodium cholate and potassium cholate, and the amino acid and its water-soluble salt are one or more of cysteine, phenylalanine, histidine, alanine and their sodium or potassium salts.
Wherein the structure of the amino acid is R1NHCH2CH2COOH，R1Is a C10-C20 hydrocarbyl group. The amino acid and the water-soluble salt thereof have good hydrophilic and lipophilic properties, effectively reduce the surface tension of water and are beneficial to the adhesion of a water film on the surface of an oil body.
The phosphate ester is preferably one or more of monobasic ester, dibasic ester and tribasic ester formed by phosphoric acid and alcohol such as polyethylene glycol, butanol, octanol and the like, and can be one or more of polyethylene glycol phosphate ester, butanol phosphate ester and octanol phosphate ester.
In the invention, the solvent is water or a mixture of water and alcohol, and the alcohol is one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol and butanol. When the solvent is a mixture of water and alcohol, the weight ratio of water to alcohol is 1: 0.1-1:5, preferably 1: 0.5-1:1. Preferably, the water is deionized water.
According to a preferred mode of the invention, the composition provided by the invention further comprises one or more of a fluid loss agent, an antioxidant, a bactericide, a thickening agent, a solubilizer and a pH regulator.
In the invention, the fluid loss agent is used for reducing the water evaporation of the composition after film formation, so that the film can play a role more continuously. In the invention, the fluid loss agent is preferably one or more of sodium sulfate, acrylamide, vinylpyridine and methacrylic acid. The fluid loss additive is present in an amount of from 0 to 5 wt%, preferably from 0 to 4 wt%, more preferably from 0.1 to 1.5 wt%, based on the total weight of the composition.
In the present invention, the antioxidant is used to prevent the deterioration of the film due to oxygen in the air, thereby allowing the film to more continuously function. In the invention, the antioxidant is preferably one or more of allicin, p-phenylenediamine and vitamin C. The antioxidant is contained in an amount of 0 to 10% by weight, preferably 0 to 4% by weight, more preferably 0.1 to 3.5% by weight, based on the total amount of the composition.
In the present invention, the bactericide is used to prevent the deterioration of the film due to bacteria in the air, thereby allowing the film to more continuously function. According to the invention, the bactericide is preferably one or more of isothiazolinone, sodium citrate and hydroxypropyl cellulose. The amount of the bactericide is 0 to 5% by weight, preferably 0.1 to 1% by weight, based on the total amount of the composition.
In the present invention, the thickener is used to increase the consistency of the composition, making film formation easier and the film more durable. The thickening agent is preferably one or more of polyethylene oxide, ethylene oxide ether copolymer, ethylene oxide glycoluril copolymer and polyacrylic acid. The thickener is present in an amount of 0 to 5 wt%, preferably 0.1 to 4.5 wt%, more preferably 0.1 to 0.45 wt%, based on the total weight of the composition.
In the present invention, the solubilizer is used to increase the solubility of the other components of the composition, particularly the relatively insoluble components, in the solvent. According to the invention, the solubilizer is preferably one or more of polyether, butyric acid, fatty alcohol polyoxyethylene ether, glycerol polyoxypropylene ether, sorbitol fatty acid ester and polyglycerol fatty acid ester. The content of the solubilizer is 0 to 5% by weight, preferably 0.1 to 4.5% by weight, more preferably 0.15 to 0.45% by weight, based on the total amount of the composition.
The polyether is a linear polymer prepared by ring opening homopolymerization or copolymerization of ethylene oxide, propylene oxide, butylene oxide and the like serving as raw materials under the action of a catalyst. The paint has a slightly special smell, is non-toxic and non-corrosive, has good compatibility with most organic matters, and is a non-flammable and non-explosive article; since the thermal oxidation stability of polyether is not excellent, polyether is easy to chain scission under the action of oxidation. Substances such as antioxidant vitamin C and the like are added to prevent the polyether from being oxidized and chain broken.
The polyether can obtain polyethers with different solubilities by adjusting the proportion of alkylene oxide in the molecule, wherein the higher the proportion of alkylene oxide is, the higher the solubility in water is; the water solubility is enhanced along with the reduction of the molecular weight and the increase of the proportion of the terminal hydroxyl; and vice versa; the water solubility of ethylene oxide, propylene oxide copolyethers decreases with increasing temperature.
In one embodiment, the polyether is selected from any one or a combination of more of L61, L62, L64, F38, L35, F65, L45; preferably; the polyether is selected from L64 and F65; further preferably, the weight ratio of L64 to F65 is 1: (0.5-5); more preferably, the weight ratio of L64 to F65 is 1: 3. the L64 and F65 are available, for example, from south chen runzu chemical co.
In the invention, the pH regulator is used for regulating the pH value of the composition to be about 7 so as to reduce the corrosion to equipment and the pollution to liquid organic hydrocarbon. In the invention, the pH regulator is preferably one or more of sodium tripolyphosphate, sodium bicarbonate, sodium carbonate and sodium dihydrogen phosphate. The content of the pH regulator is 0 to 10% by weight, preferably 0 to 2% by weight, based on the total amount of the composition.
According to one embodiment of the present invention, the composition may be used in combination with a solid substance such as hollow glass microspheres, so that the composition floats on the surface of the organic hydrocarbon liquid. The hollow glass microspheres are used in an amount of 1 to 50 parts by weight relative to 100 parts by weight of the above inhibitor composition. The particle size of the hollow glass microspheres or other solid matters can be randomly selected between 1 and 1000 mu m according to requirements, and the density is between 0.1 and 0.5 g/ml.
According to a preferred embodiment of the invention, the inhibitor composition mainly comprises 50-90 parts by weight of polyethylene glycol (containing C4-C200), 2-5 parts by weight of imidazoline and water-soluble salts thereof, 0.1-1 part by weight of sodium citrate and 5-20 parts by weight of deionized water.
In one embodiment, the composition comprises 5 to 50 parts by weight of water, 10 to 40 parts by weight of polyethylene glycol, 1 to 10 parts by weight of amino acids and their water-soluble salts or phosphate esters, 1 to 10 parts by weight of imidazoline and its water-soluble salts, 0.1 to 3 parts by weight of polyether and 1 to 5 parts by weight of sodium citrate.
In another embodiment, the composition comprises 10 to 30 parts by weight of an alcohol, 3 to 10 parts by weight of imidazoline, 0.5 to 2 parts by weight of a phosphate ester, 0.5 to 2 parts by weight of a polyether, 0.5 to 2 parts by weight of a fatty acid ethylene oxide adduct, 10 to 50 parts by weight of polyethylene glycol, and 1 to 10 parts by weight of sodium citrate.
In another embodiment, the composition contains 10-60 parts by weight of water, 20-60 parts by weight of polyethylene glycol, and one or more of the other substances mentioned above (fatty acid ethylene oxide adducts, phosphate esters, vitamin C, sodium citrate, polyethers, etc.).
In the composition, (1) the fatty acid ethylene oxide adduct has appropriate hydrophilicity, and can improve the spreading speed of the composition on the surface of an oil body and the water film forming capability; (2) the amino acid and the water-soluble salt thereof can reduce the surface tension of water, simultaneously can improve the stability of water in the composition and the anti-oxidation capability of the composition, and reduce the volatilization of harmful gases such as VOC (volatile organic Compounds) in oil bodies, thereby reducing the harm to workers and the pollution to the environment; (3) the phosphate and the imidazoline also have proper hydrophilic-lipophilic balance, so that the adhesion capability of the composition on the surface of an oil body and the coverage rate of the surface of the oil body are improved; (4) vitamin C has antioxidant effect, and can prevent oxidation of the composition; (5) isothiazolinone, sodium citrate and hydroxypropyl cellulose have antibacterial effects, can prevent microorganism etc. from decomposing effective constituent, and prolong shelf life.
The mechanism of action of the inhibitor composition of the present invention is presumed to be: the oleophilic group interacts with the organic hydrocarbon, and the oleophobic group enables the composition to float on the surface of the organic hydrocarbon, wherein water interacting with the oleophobic group can cover the surface of the organic hydrocarbon and can play a role in secondary sealing, but the water can slowly evaporate off with the prolonging of time. For external disturbance or damage of the inhibitor film, the inhibitor can float on the surface of the organic hydrocarbon more freely due to the lower surface tension of the inhibitor than the organic hydrocarbon material, and once the inhibitor film is damaged, the damaged part can be quickly and automatically compensated. For organic hydrocarbon molecules in the space, the inhibitor particles can adsorb hydrocarbon substances in the space onto the inhibitor particles in a collision adsorption mode, the inhibitor particles collide with each other and polymerize to form larger inhibitor molecules, and the inhibitor molecules descend by gravity and finally remove the organic hydrocarbon substances in the space, so that the effect of effectively inhibiting the volatilization of the organic hydrocarbon for a long time is achieved.
The inhibitor composition provided by the invention is simple in preparation method, and only the components are required to be uniformly mixed.
In a second aspect, the present invention provides a method for inhibiting the volatilization of a liquid organic hydrocarbon, which comprises atomizing the above composition into particles having a particle size of 1nm to 100 μm, and then allowing the particles to settle or to be externally applied to the surface of the organic hydrocarbon liquid.
The particles with the particle size of 1nm-100 mu m are more beneficial to the volatilization inhibition of organic hydrocarbon substances and the volatilization of VOC gas, thereby reducing the harm to workers and the pollution to the environment; on the other hand, when the granular spray is attached to the surface of an organic hydrocarbon substance, the granular spray is not easy to form sedimentation and fall off, secondary pollution is caused, the use efficiency of the inhibitor is improved, and waste is avoided. Accordingly, the particle size of the control inhibitor composition of the present invention is 1nm to 100. mu.m, preferably 300nm to 100. mu.m, more preferably 500nm to 50 μm, and still more preferably 800nm to 50 μm. The particle diameter in the present invention means a particle diameter.
In the present invention, the liquid organic hydrocarbon refers to organic hydrocarbon substances which are liquid under storage and/or transportation conditions, such as aliphatic hydrocarbons and/or aromatic hydrocarbons of C4-C23.
In the present invention, the inhibitor composition can be atomized into the particles with the above particle size by various atomization methods, preferably, by pressure atomization, rotary disc atomization, electrostatic atomization, gas atomization or sonic atomization.
In the present invention, the particles may be settled or delivered to the surface of the organic hydrocarbon liquid by gravity settling or by external force.
In one embodiment, solid floating materials such as hollow glass microspheres with oleophobic surfaces are prepared or purchased, the solid floating materials are brought to the surface of the liquid organic hydrocarbon in a mode of external air flow and the like, when the solid floating materials cover most of the surface of the liquid organic hydrocarbon, the atomized inhibitor composition acts on the surface of the liquid organic hydrocarbon to form a solid-liquid co-sealed liquid organic hydrocarbon surface, and therefore the longer volatilization inhibition effect is achieved.
In the present invention, since the atomized particles are small and strong and durable, the composition is used in an amount sufficient to form a thin coating on the surface of the organic hydrocarbon liquid to completely cover the surface of the organic hydrocarbon liquid. Preferably, the composition is used in an amount such that the thickness of the particles at the surface of the organic hydrocarbon liquid is between 1nm and 150 μm, preferably between 600nm and 120 μm, more preferably between 900nm and 100 μm. Typically, the composition is used in an amount of from 10 to 100g per square meter of surface of the stored organic hydrocarbon liquid. The amount is much less than the amount of prior art surfactants above 1000 g.
The invention will now be further illustrated by the following examples. In the following examples, the reagents/starting materials are all commercially available unless otherwise indicated.
Imidazoline was purchased from commercially available products of Biotech, Inc., Bangkong;
PEG4000, PEG6000 and PEG8000 are all commercially available products from the Haian petrochemical plant of Jiangsu province;
glycerol polyoxypropylene ether was purchased from Nantong Boya environmental protection science and technology Limited under the trademark GP 330;
the polyacrylic acid is a commercial product with the trademark of S861172 of Shanghai Hongshun biological technology Limited.
Examples 1 to 9
The components are uniformly mixed at room temperature according to the composition shown in the table 1 to obtain the oil gas inhibitor composition. In Table 1, the parts are by weight.
Comparative examples 1 to 2
An oil and gas inhibitor composition was prepared according to the method of example 1, except that the components and proportions were as shown in table 1 below.
TABLE 1
Comparative example 3
An inhibitor composition was prepared according to the method of example 1, except that the composition was formulated as described in CN108136360A, namely 20 parts by weight PEG4000, 60 parts by weight C9 linear ethoxylate (CAS number 68439-46-3) and 20 parts by weight solvent deionized water.
Test examples 1 to 14
The hydrocarbon inhibition effect of the hydrocarbon inhibitor composition was tested as follows.
A place: a gas station in Guangzhou petrochemical China;
experiment oil tank: diameter of 3 m and volume of 30m3The tank age of the oil tank is about 20 years, and 50-80 liters of gasoline is left in the tank;
air temperature conditions: local summer air temperature conditions;
humidity conditions: about 90% RH;
the atomization apparatus used: NV ST1000 nano-generator from Nanovapor corporation;
the test tank body is positioned in an external air environment without blocking, the solar radiation in noon is directly irradiated onto the tank body, and the temperature of the tank body reaches nearly 50 ℃. In addition, sundries such as soil, asbestos, wood and the like inside and outside the tank body are not particularly cleaned, so that the inside and the outside of the tank body are in a severe environment to the maximum extent.
The VOC concentration in the upper space inside the tank body is tested, the continuous test is carried out for more than 2 hours, and the VOC concentration in the tank is not changed any more. The concentrations measured at the middle detection port and the lower detection port were 83% LEL (explosion limit concentration) and 2v/v concentration, respectively.
The oil and gas inhibitor compositions of the above examples and comparative examples were atomized by an atomizer into particles having a particle size of 1 μm, and then 1L of the atomized composition was sent into a tank through an inhibitor inlet to settle on the oil surface, and the thickness of the particles on the surface of gasoline is shown in Table 2. Then, the apparatus was closed, and air was introduced into the tank to discharge the VOC in the space above the composition in the tank until the VOC concentration at the inspection port was lowered to 0, and then air introduction was stopped, and a timer was started, and the VOC concentration in the tank was measured every 0.5h, wherein the results at 2h and 120h are shown in table 2, the VOC concentration in test example 1 and the VOC concentration in test example 13 (test examples 1 to 12 were numbered in the order of the examples and comparative examples in table 1, the blank sample was test example 13, and comparative example 3 corresponds to test example 14) were changed within 120h as shown in fig. 1, the VOC concentration in test example 13 was changed within 2h as shown in fig. 2, and the VOC concentration in test example 14 was changed as shown in fig. 3.
TABLE 2
From the above results, it can be seen that, when the temperature of the tank body reaches about 50 ℃ and impurities such as soil, asbestos, wood and the like exist in the oil body in the tank body, the oil gas inhibitor composition of the present invention can still inhibit the volatilization of oil gas for a long time by using a small amount, i.e. the oil gas inhibitor composition of the present invention has a good inhibition effect on the volatilization of gasoline. The oil gas inhibitor composition does not contain silicon and/or fluorine, is green and environment-friendly, and has no pollution to the environment and no toxicity to human bodies.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. An oil and gas inhibitor composition comprises a film-forming agent, an emulsifier, a tonicity agent and a solvent, wherein the composition has a hydrophilic-lipophilic balance (HLB) of 10 to 25, preferably 15 to 20.
2. Composition according to claim 1, wherein the film-forming agent is present in an amount of 10 to 90 wt.%, preferably 50 to 90 wt.%, based on the total amount of the composition; the content of emulsifier is 1-10 wt%, preferably 2-5 wt%; the content of the tension reducer is 1-10 wt%, preferably 1-5 wt%; the content of the solvent is 1 to 70% by weight, preferably 5 to 20% by weight.
3. The composition of claim 1 or 2, wherein the film-forming agent is a polyglycol and/or a fatty acid ethylene oxide adduct.
4. The composition according to claim 3, wherein the polyglycol is polyethylene glycol, preferably polyethylene glycol having a number average molecular weight in the range of 100-10000.
5. A composition according to claim 3 or 4, wherein the fatty acid ethylene oxide adduct has a hydrophilic lipophilic balance value of 11 to 15, more preferably selected from one or more of polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monolaurate.
6. The composition of any one of claims 1-5, wherein the emulsifier is one or more of imidazoline and its water soluble salts, polyacrylamide, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; imidazoline and its water-soluble salts are preferred.
7. The composition of any one of claims 1-6, wherein the tonicity agent is one or more of amino acids and their water soluble salts, polyethylene glycol phosphate, butanol phosphate, octanol phosphate, sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium cholate, potassium cholate, and one or more of cysteine, phenylalanine, histidine, alanine, and their sodium or potassium salts.
8. The composition according to any one of claims 1 to 7, wherein the solvent is water or a mixture of water and an alcohol, and the alcohol is one or more of methanol, ethanol, ethylene glycol, propanol, propylene glycol, butanol.
9. The composition according to any one of claims 1 to 8, further comprising one or more of a fluid loss agent, an antioxidant, a bactericide, a thickener, a solubilizer and a pH regulator, wherein the fluid loss agent is one or more of sodium sulfate, acrylamide, vinyl pyridine and methacrylic acid; the antioxidant is one or more of garlicin, p-phenylenediamine and vitamin C; the bactericide is one or more of isothiazolinone, sodium citrate and hydroxypropyl cellulose; the thickening agent is one or more of polyethylene oxide, ethylene oxide ether copolymer, ethylene oxide glycoluril copolymer and polyacrylic acid; the solubilizer is one or more of polyether, butyric acid, fatty alcohol-polyoxyethylene ether, glycerol polyoxypropylene ether, sorbitol fatty acid ester and polyglycerol fatty acid ester; the pH regulator is one or more of sodium tripolyphosphate, sodium bicarbonate, sodium carbonate and sodium dihydrogen phosphate.
10. Composition according to claim 9, wherein the fluid loss additive is present in an amount of 0 to 5 wt. -%, preferably 0 to 3 wt. -%, more preferably 0.1 to 1.5 wt. -%, based on the total amount of the composition; the content of the antioxidant is 0 to 10% by weight, preferably 0 to 4% by weight, more preferably 0.1 to 3.5% by weight; the content of the bactericide is 0 to 5% by weight, preferably 0.1 to 1% by weight; the content of the thickener is 0 to 5% by weight, preferably 0.1 to 4.5% by weight, more preferably 0.1 to 0.45% by weight; the content of the solubilizer is 0 to 5% by weight, preferably 0.1 to 4.5% by weight, more preferably 0.15 to 0.45% by weight; the content of the pH adjuster is 0 to 10% by weight, preferably 0 to 2% by weight.
11. A method of inhibiting the volatilization of a liquid organic hydrocarbon which comprises atomizing the composition of any one of claims 1 to 10 into particles having a particle size of between 1nm and 100 μm and then allowing the particles to settle or be externally forced onto the surface of the organic hydrocarbon liquid.
12. A method according to claim 11, wherein the composition is atomised into particles having a size of between 500nm and 50 μm, and the particles are then allowed to settle or are subjected to an external force on the surface of the organic hydrocarbon liquid.
13. The method according to claim 11 or 12, wherein the atomization is by pressure atomization, rotary disc atomization, electrostatic atomization, gas atomization or sonic atomization.
14. A method according to any one of claims 11 to 13, wherein the particles are settled or delivered to the surface of the organic hydrocarbon liquid by gravity settling or by external force.
15. A method according to any one of claims 11 to 14, wherein the composition is used in an amount such that the particles have a thickness of between 1nm and 150 μm, preferably between 600nm and 120 μm, more preferably between 900nm and 100 μm, at the surface of the organic hydrocarbon liquid.
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| CN1302327A (en) * | 1999-01-27 | 2001-07-04 | 阿什兰公司 | Acidic composition containing fluoride for removal of photoresists and etch residues |
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| CN106520102A (en) * | 2015-09-11 | 2017-03-22 | 中国石油化工股份有限公司 | Composition for lowering viscosity of thick oil, thick oil viscosity reducer, preparation method, thick oil viscosity reduction method and thick oil reservoir production method |
| CN108136360A (en) * | 2015-09-30 | 2018-06-08 | 纳米蒸汽有限公司 | The method and composition inhibited for steam |
| CN108624313A (en) * | 2017-03-15 | 2018-10-09 | 中国石油化工股份有限公司 | For reducing the composition and heavy crude thinner and preparation method and viscosity reduction method and heavy crude reservoir recovery method of viscosity of thickened oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302327A (en) * | 1999-01-27 | 2001-07-04 | 阿什兰公司 | Acidic composition containing fluoride for removal of photoresists and etch residues |
| CN103550897A (en) * | 2013-09-29 | 2014-02-05 | 浙江工业大学 | Oil surface spreading agent |
| CN106520102A (en) * | 2015-09-11 | 2017-03-22 | 中国石油化工股份有限公司 | Composition for lowering viscosity of thick oil, thick oil viscosity reducer, preparation method, thick oil viscosity reduction method and thick oil reservoir production method |
| CN108136360A (en) * | 2015-09-30 | 2018-06-08 | 纳米蒸汽有限公司 | The method and composition inhibited for steam |
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