Voc inhibiting agent and method of inhibiting the volatilization of organic liquids containing malodorous components
By using VOCs evaporation inhibitors, the problems of evaporation and odor of volatile liquids in storage tanks have been solved, achieving safe and convenient VOCs control, which is suitable for various storage tanks and oil tanker transportation.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-11-27
- Publication Date
- 2026-05-29
AI Technical Summary
Existing technologies cannot effectively suppress the volatilization of volatile liquids in storage tanks, especially during the deformation of large storage tanks, gaps in floating roof connections, and loading processes on oil tankers, leading to excessive VOC emissions and safety hazards. Furthermore, existing floating roofs pose an accident risk.
A VOCs evaporation inhibitor is employed, which consists of hollow microspheres, surfactants, stabilizers, dispersants, coupling agents, and adsorbents. Its density is less than that of volatile liquids, enabling it to automatically cover the liquid surface and eliminate odors. Through the action of fluidity and adsorbents, it achieves complete sealing and inhibits volatilization.
It effectively reduces VOC concentration to below 1000ppm, eliminates odors, avoids tank jamming and sinking accidents, improves tank utilization, reduces safety hazards, and is suitable for various tank and oil tanker transportation processes.
Smart Images
Figure CN122098231A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of VOCs and odor source control technology, specifically to a VOCs volatilization inhibitor and a method for inhibiting the volatilization of organic liquids containing odorous components. Background Technology
[0002] Existing atmospheric pressure storage tanks for volatile liquids are classified into internal floating roof tanks, external floating roof tanks, and dome-roof tanks. Among them, dome-roof tanks lack effective source control measures and require the use of interconnected pipelines to collect VOCs before centralized treatment with oil and gas recovery devices. However, this poses a safety risk of cascading fires after the tanks are interconnected, and its continued use is no longer recommended.
[0003] External floating roof tanks can only reduce VOC emissions at the source by using external floating roofs and sealing measures. However, large tanks are prone to deformation, and existing sealing materials cannot meet the needs of the deformation space, leading to incomplete sealing of the liquid surface and large-scale VOC emissions. On the other hand, during the up-and-down movement of the floating roof and high-efficiency seals, volatile liquids remain on the inner wall of the tank. Existing sealing measures cannot suppress the evaporation of these residual liquids, thus causing VOC emissions. Internal floating roof tanks use internal floating roofs and high-efficiency seals to suppress the evaporation of volatile liquids. However, due to tank deformation, oil buildup on the inner wall of the tank, and gaps in the connection of the internal floating roof, they cannot fundamentally suppress VOCs.
[0004] The above-mentioned floating roofs cannot fully contact the oil, and flash explosions caused by the presence of oil and gas have occurred many times during use. In addition, rigid floating roofs have also experienced accidents such as jamming and sinking many times during use, so the performance of floating roofs is not ideal.
[0005] During the transportation of large oil tankers, fluctuations in the oil level generate significant amounts of VOCs. Current practice involves inerting the vapor space above the oil tanker's storage tanks; however, this method cannot completely prevent VOC generation. Particularly during loading, according to relevant standards, the oxygen content in the ship-to-shore safety docking module at the oil tanker terminal must be less than 11%. Because many oil tankers lack the capacity for inerting, the oxygen content in the cargo hold exceeds this standard, rendering the on-shore or dockside oil and gas recovery devices ineffective, resulting in excessive VOC emissions during the loading process.
[0006] The maximum design pressure of the above-mentioned atmospheric pressure storage tanks is generally slightly positive pressure, which cannot effectively suppress the volatilization of oil products, nor can it suppress the volatilization of odorous components in oil products. There is an urgent need to develop a technology that can effectively suppress VOCs by being self-flowing, completely sealed, not jamming, not settling, and adhering to the wall. Summary of the Invention
[0007] The purpose of this invention is to overcome the problems of existing technologies, such as the difficulty in effectively suppressing VOCs volatilization when storing volatile organic liquids in atmospheric pressure tanks, the potential for various accidents during the use of internal and external floating roofs, the difficulty in controlling VOCs volatilization during oil tanker loading and transportation, and the difficulty in eliminating the odor of volatile organic liquids. This invention provides a VOCs volatilization inhibitor and a method for inhibiting the volatilization of organic liquids containing odorous components. The VOCs volatilization inhibitor provided by this invention has a lower density than the volatile organic liquid containing odorous components, possesses certain fluidity and stability, and can achieve automatic coverage and complete sealing of the liquid surface, effectively preventing volatilization during storage, loading, and transportation. Furthermore, this VOCs volatilization inhibitor contains adsorbent materials that can eliminate odorous components in the volatile organic liquid.
[0008] To achieve the above objectives, the first aspect of the present invention provides a VOCs volatilization inhibitor, which contains hollow microspheres, surfactants, stabilizers, dispersants, coupling agents, adsorbents, and solvents, for inhibiting the volatilization of organic liquids containing malodorous components and eliminating the odor of organic liquids containing malodorous components.
[0009] Wherein, the density of the VOCs volatile inhibitor is less than the density of the organic liquid containing malodorous components.
[0010] Preferably, the density of the VOCs volatile inhibitor is 0.03 to 0.2 g / mL less than the density of the organic liquid containing malodorous components.
[0011] Preferably, the density of the VOCs volatile inhibitor is 0.3 to 0.6 g / mL.
[0012] Preferably, the solvent is water.
[0013] Preferably, the content of hollow microspheres is 3 to 20 parts by weight, more preferably 6 to 15 parts by weight, relative to 100 parts by weight of the solvent.
[0014] Preferably, the density of the hollow microspheres is 0.05–0.6 g / mL, and more preferably 0.1–0.3 g / mL.
[0015] Preferably, the median particle size D50 of the hollow microspheres is 5–500 μm, and more preferably 10–100 μm.
[0016] Preferably, the hollow microspheres are made of soda lime borosilicate glass.
[0017] Preferably, the content of the adsorbent material is 0.5 to 8 parts by weight relative to 100 parts by weight of the solvent, and more preferably 0.8 to 4 parts by weight.
[0018] Preferably, the adsorbent material is selected from activated carbon and / or metal-organic framework materials.
[0019] More preferably, the specific surface area of the activated carbon is 800-2000 m². 2 / g, with an average pore size of 0.4–70 nm, a total pore volume of 0.5–1.6 mL / g, and a particle size of 10–500 μm.
[0020] More preferably, the specific surface area of the metal-organic framework material is 600–1700 m². 2 / g, with an average pore size of 0.3–60 nm, a total pore volume of 0.6–2 mL / g, and a particle size of 10–500 μm.
[0021] Preferably, the surfactant content is 0.01 to 6 parts by weight, more preferably 0.03 to 2 parts by weight, relative to 100 parts by weight of the solvent.
[0022] Preferably, the surfactant is a small molecule water-soluble surfactant with a molecular weight of 200 to 800 and / or a high molecular weight water-soluble surfactant with a molecular weight of 6,000 to 20,000.
[0023] More preferably, the small molecule water-soluble surfactant is selected from at least one of sodium oleate, sodium laurylate, sodium stearate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, octadecylamine, cocoylamine, and dodecylamine.
[0024] More preferably, the high molecular weight water-soluble surfactant is selected from at least one of polyacrylate and its derivatives, polyethyleneimine, polyvinylpyrrolidone, polyacrylamide and its derivatives, polyvinyl alcohol, polyoxyethylene polyoxypropylene ether, polyvinyl ether and fatty alcohol polyoxyethylene ether.
[0025] Preferably, the content of the stabilizer is 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight, based on the weight of the solvent.
[0026] Preferably, the stabilizer is selected from cellulose compounds and / or starch.
[0027] More preferably, the cellulose compound is selected from at least one of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, and hydroxypropylmethylcellulose.
[0028] Preferably, the content of the dispersant is 0.1 to 6 parts by weight, more preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the solvent.
[0029] Preferably, the dispersant is a cationic dispersant and / or a polymeric dispersant.
[0030] More preferably, the cationic dispersant is selected from at least one of amine salts, quaternary ammonium salts, and pyridinium salts.
[0031] More preferably, the polymeric dispersant is selected from at least one of polycaprolactone polyol-polyethyleneimine block copolymer dispersants, acrylic polymeric dispersants, polyurethanes, and polyesters.
[0032] Preferably, the coupling agent content is 0.05 to 8 parts by weight, more preferably 0.2 to 4 parts by weight, relative to 100 parts by weight of the solvent.
[0033] Preferably, the coupling agent is selected from at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, and organic complexes.
[0034] Preferably, the VOCs evaporation inhibitor further contains an antibacterial agent and / or a water-retaining agent.
[0035] Preferably, based on the total weight of the VOCs volatile inhibitors, the content of the antibacterial agent is 0-1% by weight, preferably 0.04-0.2% by weight.
[0036] Preferably, the antibacterial agent is selected from at least one of quaternary ammonium salt compounds, organohalides, and pyridine salt compounds.
[0037] Preferably, the water-retaining agent is selected from at least one of n-hexadecyl alcohol, n-octadecyl alcohol, and n-butanol.
[0038] Preferably, the thickness of the water-retaining agent above the liquid surface of the VOCs volatilization inhibitor is 3-4 mm.
[0039] Preferably, the VOCs volatile inhibitor has a viscosity of <2000 cP, a conductivity of 1500–2500 PS / m, and an absolute value of 20–50 mV for its zeta potential.
[0040] Preferably, the odorous organic liquid is a petroleum product, preferably light crude oil.
[0041] A second aspect of the present invention provides a method for suppressing the volatilization of organic liquid containing malodorous components, the method comprising: delivering the aforementioned VOCs volatilization inhibitor above the surface of the organic liquid containing malodorous components.
[0042] Compared with the prior art, the present invention has at least the following advantages:
[0043] (1) The VOCs volatile inhibitor provided by this invention mainly consists of high-strength, low-density hollow microspheres and solvents, combined with surfactants, stabilizers, dispersants, coupling agents, and adsorbents. The resulting VOCs volatile inhibitor is a fluid floating material that can effectively cover and float above volatile organic liquids containing odorous components. Specifically, the density of the VOCs volatile inhibitor is less than that of the volatile organic liquid containing odorous components, and it has a certain degree of fluidity and stability, enabling automatic coverage of the surface of the volatile organic liquid. At the same time, the adsorbents contained in the VOCs volatile inhibitor can eliminate the odor in the organic liquid containing odorous components. The VOCs volatile inhibitor itself does not contain volatile VOCs materials and has the characteristics of low vapor pressure, low viscosity, low density, low air permeability, and strong stability. It also possesses fluidity, conductivity, flame retardancy, and oleophobicity. Most importantly, in the preferred case, when the solvent is water, the VOCs volatile inhibitor provided by the present invention is mainly composed of inorganic components, and is immiscible with organic liquids containing malodorous components, so it will not affect the quality of various organic liquids during use.
[0044] (2) In practical application, the method for suppressing the volatilization of organic liquids containing odorous components is simple to operate. It only requires delivering the VOCs volatile inhibitor to the surface of the volatile organic liquid containing odorous components using conventional methods, such as pumping or other means. This VOCs volatile inhibitor can flow freely and spread over the organic liquid containing odorous components, providing complete coverage without any dead zones. This VOCs volatile inhibitor can fluctuate with the liquid level of the organic liquid containing odorous components (this can be called a "liquid floating board"). Compared to various metal floating boards, such as aluminum alloy floating boards, fiberglass floating boards, and fully liquid-contact floating boards, it can replace various rigid metal floating boards or be used in conjunction with existing fully liquid-contact floating boards.
[0045] (3) After using the VOCs evaporation inhibitor of the present invention, the concentration of VOCs above the surface of the organic liquid containing odorous components is always less than 1000 ppm (even less than 10 ppm), which is far less than the 2000 ppm requirement for fugitive emissions. Existing internal floating roof tanks have various floating roofs that move up and down, leaving organic liquid residue on the inner wall of the tank, thus causing VOCs to evaporate. With the VOCs evaporation inhibitor of the present invention, during the rise or fall of the liquid level, the inhibitor prevents the liquid from adhering to the inner wall of the tank. Because the inhibitor leaves a layer on the inner wall, and the volatile organic liquid containing odorous components is immiscible with the inhibitor, it is difficult for the liquid containing odorous components to adhere to the inner wall of the tank. This solves the problem of VOCs concentration exceeding the standard due to the adhesion of volatile liquid containing odorous components to the inner wall, and also eliminates the odor of the organic liquid containing odorous components. Depending on actual usage requirements, the thickness of the VOCs evaporation inhibitor can be 1 cm or higher, with no height limit. This VOCs evaporation inhibitor can effectively replace various internal floating discs and efficient sealing measures, making the storage of various volatile organic liquids simpler, safer, and more convenient. During the storage stage, it can effectively reduce the amount of VOCs volatilization and eliminate the odor in organic liquids containing malodorous components. Attached Figure Description
[0046] Figure 1 This is a schematic diagram of the primary sealing of the external floating roof and the filling of the gas phase space of the rain shield with VOCs volatilization inhibitors.
[0047] Figure 2 This is a schematic diagram illustrating the use of VOCs volatile inhibitors in atmospheric pressure storage tanks such as fixed tanks and internal floating roof tanks.
[0048] Figure 3 This is a schematic diagram of the oil tanker loading or transportation process.
[0049] Figure 4 This is a SEM image of hollow microspheres.
[0050] Figure 5 This is the adsorption isotherm of powdered activated carbon A.
[0051] Figure 6 This is a zeta potential test graph of inhibitor 1 prepared in Example 1.
[0052] Figure 7 This is the adsorption isotherm of powdered activated carbon B. Detailed Implementation
[0053] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.
[0054] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0055] The VOCs volatilization inhibitor provided by this invention comprises hollow microspheres, surfactants, stabilizers, dispersants, coupling agents, adsorbents, and solvents. It is used to inhibit the volatilization of organic liquids containing odorous components and eliminate their odor. Because it contains hollow microspheres, surfactants, stabilizers, dispersants, coupling agents, and adsorbents, the VOCs volatilization inhibitor provided by this invention has the characteristics of low density, good flowability, strong stability, and excellent uniformity, and can eliminate the odor of organic liquids containing odorous components. In practical applications, as long as the density of the VOCs volatilization inhibitor is less than the density of the organic liquid containing odorous components, and it contains adsorbents, it can effectively inhibit the volatilization of the organic liquid containing odorous components and eliminate its odor.
[0056] In this invention, the density of the VOCs volatile inhibitor can be determined based on the type of organic liquid containing odorous components. In some embodiments, the organic liquid can be various petroleum products containing odorous components. In a preferred embodiment, the organic liquid containing odorous components can be light crude oil.
[0057] In some embodiments, the density of the VOCs volatile inhibitor is generally 0.03 to 0.2 g / mL less than the density of the organic liquid containing odorous components, for example, 0.03 g / mL, 0.05 g / mL, 0.08 g / mL, 0.1 g / mL, 0.12 g / mL, 0.15 g / mL, 0.18 g / mL, or 0.2 g / mL. In a preferred embodiment, when the organic liquid containing odorous components is light crude oil, the density of the VOCs volatile inhibitor is 0.3 to 0.6 g / mL.
[0058] In this invention, the density of the VOCs volatile inhibitor can be controlled by controlling the content of the solvent and other components. In the VOCs volatile inhibitor of this invention, in order not to affect the quality of the organic liquid containing odorous components, in a preferred embodiment, the solvent is water.
[0059] In the VOCs volatile inhibitor described in this invention, the hollow microspheres are the main component, and their content and density have a significant impact on the density of the VOCs volatile inhibitor. In some embodiments, the content of the hollow microspheres relative to 100 parts by weight of the solvent can be 3 to 20 parts by weight, preferably 6 to 15 parts by weight. In other embodiments, the density of the hollow microspheres can be 0.05 to 0.6 g / mL, preferably 0.1 to 0.3 g / mL.
[0060] In this invention, the hollow microspheres are preferably made of inorganic materials to ensure that the main component of the VOCs volatile inhibitor is inorganic, making the VOCs volatile inhibitor immiscible with the organic liquid containing odorous components, thereby not affecting the quality of the volatile organic liquid containing odorous components. In one embodiment, the hollow microspheres can be made of borosilicate glass.
[0061] In some embodiments, the median particle size D50 of the hollow microspheres can be 5 to 500 μm, preferably 10 to 100 μm.
[0062] In the VOCs volatile inhibitor of the present invention, the content of the adsorbent material is 0.5 to 8 parts by weight, preferably 0.8 to 4 parts by weight, relative to 100 parts by weight of the solvent. In the present invention, the adsorbent material can be any material capable of removing odorous components volatilized from organic liquids. In a preferred embodiment, the adsorbent material is activated carbon and / or metal-organic frameworks (MOFs). In one embodiment, the specific surface area of the activated carbon is 800 to 2000 m². 2 The average pore size is 0.4–70 nm, the total pore volume is 0.5–1.6 mL / g, and the particle size is 10–500 μm. In another embodiment, the specific surface area of the metal-organic framework material is 600–1700 m² / g. 2 / g, with an average pore size of 0.3–60 nm, a total pore volume of 0.6–2 mL / g, and a particle size of 10–500 μm.
[0063] In the VOCs evaporation inhibitor of the present invention, the content of the surfactant is 0.01 to 6 parts by weight, preferably 0.03 to 2 parts by weight, relative to 100 parts by weight of the solvent. In some embodiments, the surfactant may be a small molecule water-soluble surfactant with a molecular weight of 200 to 800 and / or a high molecular weight water-soluble surfactant with a molecular weight of 8000 to 20000. In some preferred embodiments, the small molecule water-soluble surfactant may be selected from at least one of sodium oleate, sodium laurate, sodium stearate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, octadecylamine, cocoylamine, and dodecylamine. In other preferred embodiments, the high molecular weight water-soluble surfactant is selected from at least one of polyacrylate and its derivatives, polyethyleneimine, polyvinylpyrrolidone, polyacrylamide and its derivatives, polyvinyl alcohol, polyoxyethylene polyoxypropylene ether, polyvinyl ether, and fatty alcohol polyoxyethylene ether.
[0064] In the VOCs evaporation inhibitor described in this invention, the content of the stabilizer can be 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on the weight of the solvent. In some preferred embodiments, to make the organic liquid evaporation inhibitor more stable and more effectively suppress the evaporation of organic liquids, the stabilizer is selected from cellulosic compounds and / or starch. In some specific embodiments, the cellulosic compound can be selected from at least one of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, and hydroxypropylmethylcellulose.
[0065] In the VOCs evaporation inhibitor of the present invention, the content of the dispersant is 0.1 to 6 parts by weight, preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the solvent. In some preferred embodiments, in order to improve the uniformity of the organic liquid evaporation inhibitor, further improve the covering effect of the organic liquid evaporation inhibitor on the organic liquid, and reduce the evaporation of the organic liquid, the dispersant is a cationic dispersant and / or a polymeric dispersant. In some embodiments, the cationic dispersant is selected from at least one of amine salts, quaternary ammonium salts, and pyridinium salts. In other embodiments, the polymeric dispersant is selected from at least one of polycaprolactone polyol-polyethyleneimine block copolymer dispersants, acrylic polymeric dispersants, polyurethanes, and polyesters.
[0066] In the VOCs evaporation inhibitor of the present invention, the content of the coupling agent relative to 100 parts by weight of the solvent can be 0.05 to 8 parts by weight, preferably 0.2 to 4 parts by weight. In the present invention, the coupling agent can be a conventional choice in the art. In some embodiments, the coupling agent is selected from at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, and organic complexes.
[0067] In this invention, the VOCs volatile inhibitor may also contain antibacterial agents and / or water-retaining agents.
[0068] To enhance the antibacterial effect of the VOCs volatile inhibitor, the VOCs volatile inhibitor may contain an antibacterial agent. In some embodiments, based on the total weight of the VOCs volatile inhibitor, the content of the antibacterial agent may be 0-1% by weight, preferably 0.04-0.2% by weight. In a more preferred embodiment, the antibacterial agent may be at least one of a quaternary ammonium salt compound, an organohalide, or a pyridinium salt compound.
[0069] To reduce solvent loss, especially water evaporation, in the VOCs volatile inhibitor, maintain its stability, and improve its long-term effectiveness against organic liquids containing malodorous components, the VOCs volatile inhibitor may contain a water-retaining agent. In some embodiments, the water-retaining agent is selected from at least one of n-hexadecyl alcohol, n-octadecyl alcohol, and n-butanol. In a more preferred embodiment, the thickness of the water-retaining agent above the surface of the VOCs volatile inhibitor liquid may be 3–4 mm.
[0070] The VOCs volatile inhibitor provided by this invention, in addition to its low density and ability to remove odors from malodorous organic liquids, also features low volatility, low viscosity, good conductivity, good flame retardancy, good oleophobicity, and good stability. In some embodiments, the VOCs volatile inhibitor has a volatility ≤3.2 kPa at 25°C, a viscosity <2000 cP, an electrical conductivity of 1500–2500 PS / m, and an absolute value of 20–50 mV for its Zeta potential.
[0071] The present invention also provides a method for preparing a VOCs volatile inhibitor. In one embodiment, the method for preparing the VOCs volatile inhibitor includes: mixing hollow microspheres, surfactants, stabilizers, dispersants, coupling agents, adsorbent materials, solvents, optional antibacterial agents, and optional water-retaining agents.
[0072] To improve the stability of the prepared VOCs volatile inhibitor, operations can be performed in a specific sequence. In a preferred embodiment, the method for preparing the VOCs volatile inhibitor includes:
[0073] (1) Add surfactant, stabilizer, dispersant and coupling agent to solvent to obtain mother liquor;
[0074] (2) Add the hollow microspheres and adsorption material to the mother liquor;
[0075] (3) Optionally, an antibacterial agent may be added to the product obtained in step (2);
[0076] (4) Optionally, the water-retaining agent is sprayed above the liquid surface of the product obtained in step (3), and the hydrophilic groups of the water-retaining agent are partially dissolved and floated in the inhibitor, while its hydrophobic groups float on the surface of the inhibitor.
[0077] In a more preferred embodiment, the method for preparing the VOCs volatile inhibitor includes:
[0078] (1) Add surfactant, stabilizer, dispersant and coupling agent to solvent, and obtain mother liquor at a rotation speed of 100 to 1000 r / min and a temperature of 40 to 95 °C;
[0079] (2) Add hollow microspheres and adsorbent material to the mother liquor and stir at a temperature of 10-70℃ and a speed of 100-2000r / min;
[0080] (3) Optionally, an antibacterial agent may be added to the product obtained in step (2);
[0081] (4) Optionally, the water-retaining agent is sprayed above the liquid surface of the product obtained in step (3), and the hydrophilic groups of the water-retaining agent are partially dissolved and floated in the inhibitor, while its hydrophobic groups float on the surface of the inhibitor.
[0082] The density of the VOCs volatilization inhibitor prepared according to the method of the present invention needs to be determined based on the organic liquid containing malodorous components to be suppressed. If the volatilization of VOCs in light crude oil is effectively suppressed, the density of the prepared VOCs volatilization inhibitor is preferably less than 0.6 g / mL.
[0083] The VOCs evaporation inhibitor prepared by this invention is particularly suitable for volatile light crude oil; applicable applications include fixed-roof tanks and internal floating-roof tanks (horizontal tanks, vertical tanks, underground tanks, and oil storage caverns); it can be used to replace existing floating roofs and high-efficiency seals, or only to replace high-efficiency seals. During ship transportation, the VOCs evaporation inhibitor is placed above the level of the transported oil, and even with sea turbulence during transportation, VOCs will not evaporate. During oil tanker loading, the VOCs evaporation inhibitor floats above the oil, inhibiting the loading process and even eliminating the need for oil vapor recovery treatment devices, while also eliminating odors; the original air in the ship's hold can be directly discharged into the atmosphere without causing atmospheric pollution.
[0084] This invention also provides a method for suppressing the volatilization of organic liquids containing odorous components, the method comprising: conveying the aforementioned VOCs volatilization inhibitor to the surface of the organic liquid containing odorous components. The VOCs volatilization inhibitor and the method for suppressing the volatilization of organic liquids containing odorous components described in this invention can be used in fixed-roof tanks, in ship cabins, and in external floating roof tanks.
[0085] In the first embodiment, when used in a small fixed-roof storage tank, the VOCs evaporation inhibitor is first pumped into the tank. Then, volatile organic liquid containing odorous components is supplied to the tank via existing pipelines. Due to the buoyancy of the volatile organic liquid, the VOCs evaporation inhibitor naturally floats above the liquid surface, adhering tightly to the tank wall and completely covering the entire surface, thus effectively inhibiting the volatilization of VOCs from the volatile organic liquid. As the oil level fluctuates due to feeding or discharging, the VOCs evaporation inhibitor moves with the organic liquid, maintaining a tight bond with the tank wall and liquid surface. Furthermore, the overall structure of the VOCs evaporation inhibitor is not damaged by the liquid level fluctuations, thus effectively inhibiting the volatilization of the odorous organic liquid.
[0086] In the second embodiment, when used inside the ship's hold, the VOCs evaporation inhibitor is first pumped into the hold, followed by loading of the volatile organic liquid containing odorous components. Under the buoyancy of the volatile organic liquid, the VOCs evaporation inhibitor naturally floats above the surface, completely covering the entire surface. It rises with the liquid level, effectively inhibiting the volatilization of VOCs and removing the odor. During oil tanker transport, the liquid level fluctuates with the waves, and the VOCs evaporation inhibitor fluctuates accordingly, completely suppressing the volatilization of VOCs from the volatile organic liquid.
[0087] In the third embodiment, refer to Figure 2 In large external floating roof tanks, the external floating roof, primary seal, and skimmer structure effectively prevent the evaporation of organic liquids. When the large external floating roof tank deforms or the elastic deformation of the primary seal is insufficient to maintain a fully sealed contact, VOCs will inevitably escape from the gaps. In this case, filling the space below the skimmer and above the primary seal with VOC evaporation inhibitors allows the inhibitors to automatically fill the gaps when seal failure occurs, effectively solving the VOC evaporation problem caused by seal failure. Figure 1 The red area represents the filling site for VOCs volatilization inhibitors.
[0088] The use of the VOCs volatile inhibitor and the method for inhibiting the volatilization of organic liquids containing malodorous components described in this invention will produce at least the following beneficial effects:
[0089] On the one hand, using organic liquid evaporation inhibitors to replace rigid floating roofs in internal floating roof tanks will eliminate jamming and sinking accidents; on the other hand, it will reduce the volume of the tank occupied by rigid floating roofs and supporting components, significantly improving the utilization rate of the oil storage volume. Figure 2This diagram illustrates the use of VOCs evaporation inhibitors in atmospheric pressure storage tanks such as fixed tanks and internal floating roof tanks. VOCs leakage in internal floating roof tanks can be categorized into four types: wall adhesion loss, sealing loss, floating roof accessory loss, and floating roof gap loss. Among these, wall adhesion loss is currently unsolvable due to significant safety hazards associated with interconnecting tanks; sealing loss, caused by tank deformation and seal failure leading to VOCs leakage in gaps, is also unsolvable due to the difficulty in restoring the deformed tank; floating roof accessory loss is also caused by unreliable and easily failed accessories; and floating roof gap loss, caused by loose bolt connections in the internal floating roof, can be addressed by methods such as full welding. The VOCs evaporation inhibitor in this invention can replace the rigid floating roof, preventing the formation of a gas phase space between the floating roof and the liquid surface, thus achieving intrinsic safety. Replacing the fully wetted floating roof and high-efficiency seals with VOCs evaporation inhibitors can effectively solve the problem of localized VOCs leakage caused by tank deformation and seal failure. Meanwhile, the VOCs evaporation inhibitor can cover the oil adhering to the tank wall, completely solving the VOCs leakage problem caused by oil adhering to the inner wall of the floating roof. In summary, three of the four types of VOCs leakage problems are difficult to solve. If the fully liquid-contact oleophobic VOCs evaporation inhibitor of this invention is used, the following problems are solved: wall adhering loss (oil cannot continue to adhere to the tank wall due to the presence of the oleophobic inhibitor material), gap loss (no gaps), floating roof accessories (no accessories), and sealing loss (the inhibitor is in full contact with the tank wall and oil). The VOCs leakage can be directly reduced from 25% VOL% to below 1000 ppm, effectively solving the problem of excessive VOCs emissions from internal floating roof tanks.
[0090] Secondly, in the application of large external floating roof tanks, VOCs volatilization inhibitors can be filled in the space below the skid plate and above the primary seal. When gaps appear due to seal failure, the VOCs volatilization inhibitors can automatically fill the gaps, effectively combining with the existing external floating roof, thereby solving the VOCs volatilization problem caused by seal failure.
[0091] Thirdly, when used inside the cabin ( Figure 3 The VOCs evaporation inhibitor floats naturally above the liquid surface and completely covers it. During oil loading and unloading, the VOCs evaporation inhibitor rises with the oil level, effectively inhibiting the volatilization of VOCs from odorous and volatile liquids. During oil tanker transportation, the oil level fluctuates with the waves, and the VOCs evaporation inhibitor fluctuates with the level, completely suppressing the volatilization of VOCs from the oil.
[0092] The following examples further illustrate the VOCs volatile inhibitor and the method for inhibiting the volatilization of organic liquids containing malodorous components described in this invention. These examples are implemented based on the technical solution of this invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of this invention is not limited to the following examples.
[0093] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.
[0094] Surfactants that can be selected include Dow Chemical's OROTAN 731A (polyacrylate), Taiwan Chang Chun's BP 24S, BASF's Polymin SN, and BASF's Lutensol TO-8.
[0095] Hydroxyethyl cellulose can be selected from Akzo's EBS451FQ or Shin-Etsu's HX6000YG4.
[0096] Hydroxypropyl cellulose can be sourced from Aslan's HF Pharm.
[0097] Hydroxypropyl methylcellulose can be sourced from Aslan's E4M Pharm;
[0098] Dispersants that can be selected include Evonik's TEGO Dispers 755W (polyacrylic acid), BASF's Disepex AA4040AS, and Sinopco's SN-THICKENER 5040A;
[0099] Evonik's Dynasylan 4148 can be used as a silane coupling agent;
[0100] Organohalogenated antibacterial agents such as Dow Chemical's AMBERLITE KATHON LXE, whose main component is 5-chloro-2-methyl-4-isothiazolidin-3-one, can be selected.
[0101] Hollow microspheres are made of soda lime borosilicate glass material. HL15 (median particle size D50 of 80 μm, true density of 0.15 g / mL, hollow internal structure) from Zhengzhou Shenglait Hollow Microsphere New Material Co., Ltd., or K20HS (true density of 0.2 g / mL, hollow internal structure) from 3M brand can be selected.
[0102] MOF materials: KAUST-8 and ZIF-8. KAUST-8 has a specific surface area of 1236 m². 2 / g, pore volume 0.81mL / g, pore size 1.6nm, median particle size D50 100μm; ZIF-8 has a specific surface area of 1845m². 2 / g, pore volume 0.41mL / g, pore size 0.4nm, median particle size D50 is 70μm.
[0103] Activated carbon powder: Powdered activated carbon A and activated carbon B from Tianjin Carbon Membrane Technology. Activated carbon A has a specific surface area of 1880 m². 2 / g, pore volume 1.57mL / g, pore size 3.3nm, median particle size D50 65μm; specific surface area of activated carbon B 1785m² 2 / g, pore volume 0.84mL / g, pore size 1.89nm, median particle size D50 is 70μm.
[0104] Example 1
[0105] The preparation process of inhibitors:
[0106] (1) Take 1500g of deionized water, and add 0.18g of polyacrylate (OROTAN 731A from Dow Chemical), 0.43g of polyvinyl alcohol (BP 24S from Chang Chun, Taiwan), 4g of hydroxyethyl cellulose (EBS451FQ from Akzo), and 3.5g of hydroxypropyl methylcellulose (E4MPharm from Aslan) in sequence. Heat in an 80℃ water bath and stir at 300r / min for 30min. Then, add 20g of polyacrylic acid dispersant (TEGO Dispers 755W from Evonik) and continue stirring for 100min. Finally, cool to room temperature to obtain a viscous liquid.
[0107] (2) Add 25g of silane coupling agent (Evonik's Dynasylan 4148) to the viscous liquid to reduce the viscosity of the solution and increase the stability of the solution to obtain the mother liquor.
[0108] (3) Weigh 175g of hollow microspheres (HL15 from Zhengzhou Shenglait Hollow Microsphere New Material Co., Ltd.) Figure 4 (Scanning electron microscope image of hollow microspheres) and 35g powdered activated carbon A ( Figure 5 The adsorption isotherm of activated carbon A was added to the mother liquor, and the two were premixed at 100 r / min at room temperature. Then, the mixture was stirred at 1800 r / min for 15 min to uniformly disperse the hollow microspheres and powdered activated carbon A into the mother liquor, thus obtaining the inhibitor.
[0109] (4) In order to further reduce the impact of microorganisms on the quality of the inhibitor, 1g of antibacterial agent (Dow Chemical's AMBERLITE KATHON LXE) was added to the inhibitor, and finally inhibitor 1 was obtained.
[0110] Analysis showed that inhibitor 1 had a density of 0.56 g / mL, a viscosity of 1242 cP, and an absolute zeta potential of 40.6 mV. Figure 6 It has an electrical conductivity of 1793 PS / m and exhibits good fluidity, conductivity, and stability.
[0111] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0112] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour Inhibitor 1 onto the surface of the crude oil, ensuring it spreads completely and maintaining a thickness of approximately 3cm. Place the bottle in a 50℃ water bath and leave it open for 4 hours. The VOC concentration in the gaseous space above the liquid surface is measured at 323ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, which displays 32. After covering the bottle and leaving it open for 24 hours, the VOC concentration in the gaseous space above the liquid surface is measured at 532ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, which displays 34. After covering the bottle and leaving it open for one week, the VOC concentration in the gaseous space is 562ppm, with no obvious odor. The odor monitoring device is used again, and the reading remains within the range of 34, indicating stable inhibitor properties. Therefore, this inhibitor has a good effect on inhibiting VOC volatilization and eliminating odors.
[0113] Example 2
[0114] The preparation process of inhibitors:
[0115] (1) Take 1500g of deionized water, and add 0.4g of polyethyleneimine (BASF's Polymin SN), 0.2g of fatty alcohol polyoxyethylene ether (BASF's Lutensol TO-8), 2.5g of hydroxyethyl cellulose (Shin-Etsu HX6000YG4), and 4.5g of hydroxypropyl cellulose (Aslan's HF Pharm) in sequence. Heat in an 80℃ water bath and stir at 300r / min for 30min. Then, add 18g of polyacrylic acid dispersant (BASF's Disepex AA 4040AS) and continue stirring for 100min. Finally, cool to room temperature to obtain a viscous liquid.
[0116] (2) Add 21g of silane coupling agent (Evonik's Dynasylan 4148) to the viscous liquid to reduce the viscosity of the solution and increase the stability of the solution to obtain the mother liquor.
[0117] (3) Weigh 160g of hollow microspheres (HL15 from Zhengzhou Shenglait Hollow Microsphere New Material Co., Ltd.) and 40g of powdered activated carbon A, add them to the mother liquor, and premix them at 100r / min at room temperature. Then stir at 1800r / min for 15min to uniformly disperse the hollow microspheres and activated carbon A into the mother liquor to obtain the inhibitor.
[0118] (4) To further reduce the impact of microorganisms on the quality of the inhibitor, 1.5g of antibacterial agent (Dow Chemical's AMBERLITE KATHON LXE) was added to the inhibitor, and finally inhibitor 2 was obtained.
[0119] Analysis showed that inhibitor 2 had a density of 0.54 g / mL, a viscosity of 1231 cP, an absolute value of 43.6 mV for zeta potential, and a conductivity of 1653 PS / m, exhibiting good flowability, conductivity, and stability.
[0120] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0121] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour inhibitor 2 onto the surface of the light crude oil, ensuring it spreads completely and that the inhibitor thickness is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured to be 431ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 34. After the bottle is capped and left for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured to be 487ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 35. After the bottle is capped and left for one week, the VOCs concentration in the gas phase is 621ppm, with no obvious odor. The odor monitoring device is used again, and the reading remains within 35, indicating that the inhibitor is stable. Therefore, this inhibitor has a good effect on inhibiting VOCs volatilization and eliminating odors.
[0122] Example 3
[0123] The preparation process of inhibitors:
[0124] (1) Take 1500g of deionized water, and add 0.3g of polyacrylate (OROTAN 731A from Dow Chemical), 0.45g of fatty alcohol polyoxyethylene ether (lutensol TO-8 from BASF), 5g of hydroxypropyl cellulose (HFPharm from Aslan), and 3g of hydroxypropyl methylcellulose (E4MPharm from Aslan) in sequence. Heat in an 80℃ water bath and stir at 300r / min for 30min. Then, add 18g of polyacrylic acid dispersant (SN-THICKENER 5040A from Sanopco) and continue stirring for 100min. Finally, cool to room temperature to obtain a viscous liquid.
[0125] (2) Add 25g of silane coupling agent (Evonik's Dynasylan 4148) to the viscous liquid to reduce the viscosity of the solution and increase the stability of the solution to obtain the mother liquor.
[0126] (3) Weigh 165g of hollow microspheres (3M brand K20HS, true density 0.2g / mL, hollow internal structure) and 40g of powdered activated carbon A, add them to the mother liquor, and premix them at 100r / min at room temperature. Then stir at 1800r / min for 15min to uniformly disperse the hollow microspheres and activated carbon A into the mother liquor to obtain the inhibitor.
[0127] (4) To further reduce the impact of microorganisms on the quality of the inhibitor, 1.2g of antibacterial agent (Dow Chemical's AMBERLITE KATHON LXE) was added to the inhibitor, and finally inhibitor 3 was obtained.
[0128] Analysis showed that inhibitor 3 had a density of 0.55 g / mL, a viscosity of 1041 cP, an absolute value of zeta potential of 41.6 mV, and a conductivity of 1671 PS / m, exhibiting good fluidity, conductivity, and stability.
[0129] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0130] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour inhibitor 3 onto the surface of the light crude oil, ensuring it spreads completely and that the inhibitor thickness is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured to be 561ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 38. After the bottle is capped and left for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured to be 591ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 36. After the bottle is capped and left for one week, the VOCs concentration in the gas phase is 632ppm, with no obvious odor. The odor monitoring device is used again, and the reading remains within 37, indicating that the inhibitor is stable. Therefore, this inhibitor has a good effect on inhibiting VOCs volatilization and eliminating odors.
[0131] Example 4
[0132] The preparation process of inhibitors:
[0133] The method of Example 3 was implemented, except that the amount of polyacrylic acid dispersant added in step (1) was adjusted to 25g, and finally inhibitor 4 was obtained.
[0134] Analysis showed that inhibitor 4 had a density of 0.57 g / mL, a viscosity of 1186 cP, a conductivity of 1943 PS / m, and an absolute value of 29.4 mV for its zeta potential, exhibiting good fluidity, conductivity, and stability.
[0135] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0136] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour inhibitor 4 onto the surface of the light crude oil, ensuring it spreads completely and that the inhibitor thickness is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured to be 368ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 30. After the bottle is capped and left for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured to be 452ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 36. After the bottle is capped and left for one week, the VOCs concentration in the gas phase is 530ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 34. It is evident that this inhibitor has a good effect on inhibiting VOCs volatilization and eliminating odors.
[0137] Example 5
[0138] The preparation process of inhibitors:
[0139] The method of Example 1 was implemented, except that the amount of hydroxyethyl cellulose added in step (1) was adjusted to 3.5g, the amount of hydroxypropyl methyl cellulose added was adjusted to 4g, and the amount of polyacrylic acid dispersant added was adjusted to 23g, and finally inhibitor 5 was obtained.
[0140] Analysis showed that inhibitor 5 had a density of 0.57 g / mL, a viscosity of 1424 cP, an absolute value of 35.8 mV for zeta potential, and a conductivity of 1693 PS / m, exhibiting good flowability, conductivity, and stability.
[0141] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0142] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour Inhibitor 5 onto the surface of the light crude oil, with an inhibitor thickness of approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured to be 648ppm, with no obvious odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 34. After the bottle is capped and left for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured to be 862ppm, with no obvious odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 41. After the bottle is capped and left for one week, the VOCs concentration in the gas phase is 975ppm, with no obvious odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 39.
[0143] Example 6
[0144] The preparation process of inhibitors:
[0145] The method of Example 1 was implemented, except that the amount of hollow microspheres used in step (3) was adjusted to 165g and the amount of activated carbon A used was adjusted to 45g, and finally inhibitor 6 was obtained.
[0146] Analysis showed that inhibitor 6 had a density of 0.58 g / mL, a viscosity of 1568 cP, an absolute value of zeta potential of 41.3 mV, and a conductivity of 1714 PS / m, exhibiting good flowability, conductivity, and stability.
[0147] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0148] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour inhibitor 6 onto the surface of the light crude oil, ensuring it spreads completely and that the inhibitor thickness is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured to be 497ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 38. After the bottle is capped and left for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured to be 672ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 42. After the bottle is capped and left for one week, the VOCs concentration in the gas phase is 731ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 40. The inhibitor is stable. This inhibitor has a good effect on inhibiting VOCs volatilization and eliminating odors.
[0149] Example 7
[0150] The preparation process of inhibitors:
[0151] The method of Example 1 is followed, except that powdered activated carbon A in step (3) is replaced with powdered activated carbon B. Figure 7 (The adsorption isotherm of activated carbon B) was used, and the amount added was still 35g, and finally inhibitor 7 was obtained.
[0152] Analysis showed that inhibitor 7 had a density of 0.55 g / mL, a viscosity of 1185 cP, an absolute value of zeta potential of 41.3 mV, and a conductivity of 1714 PS / m, exhibiting good flowability, conductivity, and stability.
[0153] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0154] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour the inhibitor 7 onto the surface of the crude oil, ensuring it spreads completely and that the inhibitor thickness is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured to be 319ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 34. After the bottle is capped and left for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured to be 486ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 36. After the bottle is capped and left for one week, the VOCs concentration in the gas phase is 497ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 35. The inhibitor is stable. This inhibitor has a good effect on inhibiting VOCs volatilization and eliminating odors.
[0155] Example 8
[0156] The preparation process of inhibitors:
[0157] The method of Example 1 was implemented, except that the activated carbon A in step (3) was changed to MOF material ZIF-8, and the amount added was still 35g, and finally inhibitor 8 was obtained.
[0158] Analysis showed that inhibitor 8 had a density of 0.55 g / mL, a viscosity of 1096 cP, an absolute value of 38.4 mV for zeta potential, and a conductivity of 1623 PS / m, exhibiting good flowability, conductivity, and stability.
[0159] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0160] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour Inhibitor 8 onto the surface of the light crude oil, ensuring it spreads completely and measuring a thickness of approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase above the liquid surface is measured at 287ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 30. After covering the bottle and leaving it for 24 hours, the VOCs concentration in the gas phase above the liquid surface is measured at 486ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 35. After covering the bottle and leaving it for one week, the VOCs concentration in the gas phase is 497ppm, with no obvious odor. The odor concentration is measured using an odor monitoring device, and the instrument displays 37. The inhibitor is stable. This inhibitor has a good effect on inhibiting VOCs volatilization and eliminating odors.
[0161] Example 9
[0162] The preparation process of inhibitors:
[0163] The method of Example 1 was implemented, except that the powdered activated carbon A in step (3) was changed to MOF material KAUST-8, and the amount added was still 35g, and finally inhibitor 9 was obtained.
[0164] Analysis showed that inhibitor 9 had a density of 0.55 g / mL, a viscosity of 1086 cP, an absolute value of 35.7 mV for zeta potential, and a conductivity of 1621 PS / m, exhibiting good flowability, conductivity, and stability.
[0165] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0166] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour inhibitor 9 onto the surface of the light crude oil, and after it has completely spread on the surface, measure and ensure that the inhibitor thickness is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase space above the liquid surface is measured to be 453ppm, with no obvious odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 36. After leaving the bottle covered for 1 week, the VOCs concentration in the gas phase space is 678ppm, with no obvious odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 38.
[0167] Example 10
[0168] The preparation process of inhibitors:
[0169] The method of Example 1 was implemented, except that the amount of powdered activated carbon B added in step (3) was adjusted to 15g, and finally inhibitor 10 was obtained.
[0170] Analysis showed that inhibitor 10 had a density of 0.54 g / mL, a viscosity of 1424 cP, an absolute value of zeta potential of 35.6 mV, and a conductivity of 1203 PS / m, exhibiting good flowability, conductivity, and stability.
[0171] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0172] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour Inhibitor 10 onto the surface of the light crude oil. After it has completely spread on the surface of the crude oil, measure and ensure that the thickness of the inhibitor is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. The VOCs concentration in the gas phase space above the liquid surface is measured to be 385ppm, with no obvious odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 32. After leaving it covered for 24 hours, the VOCs concentration in the gas phase space above the liquid surface is measured to be 483ppm, with a slight odor. The odor concentration value is measured using an odor monitoring device, and the instrument displays 62.
[0173] Example 11
[0174] The preparation process of inhibitors:
[0175] The method of Example 1 was implemented, except that the amount of activated carbon A added in step (3) was adjusted to 65g, and finally inhibitor 11 was obtained.
[0176] Analysis showed that inhibitor 11 had a density of 0.58 g / mL and a viscosity of 1032 cP, indicating good fluidity; the absolute value of the zeta potential was 33.3 mV.
[0177] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0178] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density 0.61g / mL). Then pour Inhibitor 11 onto the surface of the light crude oil. After it has completely spread on the surface of the crude oil, measure and ensure that the thickness of the inhibitor is approximately 3cm. Place the wide-mouth bottle in a 50℃ water bath and leave it open for 4 hours. Measure the VOCs concentration in the gas phase space above the liquid surface. The concentration is 855ppm, with no obvious odor. Use an odor monitoring device to measure the odor concentration value; the instrument displays 33.
[0179] Comparative Example 1
[0180] The method of Example 1 was followed, except that hollow microspheres and adsorbent material (powdered activated carbon A) were not added.
[0181] The preparation process of inhibitors:
[0182] (1) Take 1500g of deionized water, and add 0.18g of polyacrylate (OROTAN 731A from Dow Chemical), 0.43g of polyvinyl alcohol (BP 24S from Chang Chun, Taiwan), 4g of hydroxyethyl cellulose (EBS451FQ from Akzo), and 3.5g of hydroxypropyl methylcellulose (E4MPharm from Aslan) in sequence. Heat in an 80℃ water bath and stir at 300r / min for 30min. Then, add 20g of polyacrylic acid dispersant (TEGO Dispers 755W from Evonik) and continue stirring for 100min. Finally, cool to room temperature to obtain a viscous liquid.
[0183] (2) Add 25g of silane coupling agent (Evonik's Dynasylan 4148) to the viscous liquid to reduce the viscosity of the solution and increase the stability of the solution to obtain the mother liquor.
[0184] (3) In order to further reduce the impact of microorganisms on the quality of the inhibitor, 1g of antibacterial agent (Dow Chemical's AMBERLITE KATHON LXE) was added to the inhibitor, and finally inhibitor 12 was obtained.
[0185] Analysis revealed that the density of inhibitor 12 was 0.97 g / mL, which was too high to be used.
[0186] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0187] Take a 500mL wide-mouth bottle and measure 200mL of light crude oil (density is 0.61g / mL). Then pour inhibitor 12 above the surface of the light crude oil. Inhibitor 13 sinks to the bottom of the crude oil and cannot float to the top of the light crude oil, thus it does not inhibit the volatilization of the light crude oil.
[0188] Comparative Example 2
[0189] Take 1500g of deionized water, weigh 175g of hollow microspheres (HL15 from Zhengzhou Shenglait Hollow Microsphere New Material Co., Ltd.) and 35g of powdered activated carbon A, premix the two at 100r / min at room temperature, and then stir at 1800r / min for 15min to disperse the hollow microspheres and powdered activated carbon A into the deionized water to obtain inhibitor 13.
[0190] After 10 minutes of storage, the inhibitor 13 showed solid-liquid separation, indicating that it was unstable and could not effectively inhibit the volatilization of oil.
[0191] Comparative Example 3
[0192] The method of Example 1 was implemented, except that hollow microspheres were not added.
[0193] The preparation process of inhibitors:
[0194] (1) Take 1500g of deionized water, and add 0.18g of polyacrylate (OROTAN 731A from Dow Chemical), 0.43g of polyvinyl alcohol (BP 24S from Chang Chun, Taiwan), 4g of hydroxyethyl cellulose (EBS451FQ from Akzo), and 3.5g of hydroxypropyl methylcellulose (E4MPharm from Aslan) in sequence. Heat in an 80℃ water bath and stir at 300r / min for 30min. Then, add 20g of polyacrylic acid dispersant (TEGO Dispers 755W from Evonik) and continue stirring for 100min. Finally, cool to room temperature to obtain a viscous liquid.
[0195] (2) Add 25g of silane coupling agent (Evonik's Dynasylan 4148) to the viscous liquid to reduce the viscosity of the solution and increase the stability of the solution to obtain the mother liquor.
[0196] (3) Weigh 35g of powdered activated carbon A and add it to the mother liquor. At room temperature, premix the two at a speed of 100r / min. Then stir at a speed of 1800r / min for 15min to uniformly disperse the hollow microspheres and powdered activated carbon A into the mother liquor to obtain the inhibitor.
[0197] (4) In order to further reduce the impact of microorganisms on the quality of the inhibitor, 1g of antibacterial agent (Dow Chemical's AmBERLITE KATHON LXE) was added to the inhibitor, and finally inhibitor 14 was obtained.
[0198] Analysis revealed that inhibitor 12 had a density of 0.95 g / mL, which was high, resulting in obvious solid-liquid separation and making it difficult to use.
[0199] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0200] After 10 minutes of storage, the inhibitor 14 showed solid-liquid separation, indicating that it was unstable and could not effectively inhibit oil volatilization.
[0201] Comparative Example 4
[0202] The method was carried out according to Example 1, except that no adsorbent material (powdered activated carbon A) was added.
[0203] The preparation process of inhibitors:
[0204] (1) Take 1500g of deionized water, and add 0.18g of polyacrylate (OROTAN 731A from Dow Chemical), 0.43g of polyvinyl alcohol (BP 24S from Chang Chun, Taiwan), 4g of hydroxyethyl cellulose (EBS451FQ from Akzo), and 3.5g of hydroxypropyl methylcellulose (E4MPharm from Aslan) in sequence. Heat in an 80℃ water bath and stir at 300r / min for 30min. Then, add 20g of polyacrylic acid dispersant (TEGO Dispers 755W from Evonik) and continue stirring for 100min. Finally, cool to room temperature to obtain a viscous liquid.
[0205] (2) Add 25g of silane coupling agent (Evonik's Dynasylan 4148) to the viscous liquid to reduce the viscosity of the solution and increase the stability of the solution to obtain the mother liquor.
[0206] (3) Weigh 175g of hollow microspheres (HL15 from Zhengzhou Shenglait Hollow Microsphere New Material Co., Ltd.), add them to the mother liquor, and premix them at 100r / min at room temperature. Then stir at 1800r / min for 15min to evenly disperse the hollow microspheres into the mother liquor to obtain the inhibitor.
[0207] (4) In order to further reduce the impact of microorganisms on the quality of the inhibitor, 1g of antibacterial agent (Dow Chemical's AmBERLITE KATHON LXE) was added to the inhibitor, and finally inhibitor 15 was obtained.
[0208] Methods to suppress the volatilization of organic liquids containing malodorous components:
[0209] Take a 500ml wide-mouth bottle and measure 200ml of light crude oil. Then pour Inhibitor 15 onto the surface of the crude oil, ensuring it spreads completely and that the inhibitor thickness is approximately 3cm. After leaving the bottle open for 4 hours, the VOC concentration in the vapor space above the liquid surface is measured to be 437ppm. After covering the bottle and leaving it for 24 hours, the VOC concentration in the vapor space above the liquid surface is measured to be 541ppm. The odor is difficult to eliminate.
[0210] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A VOCs volatilization inhibitor, characterized in that, This VOCs evaporation inhibitor contains hollow microspheres, surfactants, stabilizers, dispersants, coupling agents, adsorbents, and solvents, and is used to inhibit the volatilization of organic liquids containing malodorous components and eliminate the odor of organic liquids containing malodorous components. Wherein, the density of the VOCs volatile inhibitor is less than the density of the organic liquid containing malodorous components.
2. The VOCs volatilization inhibitor according to claim 1, characterized in that, The density of the VOCs volatile inhibitor is 0.03–0.2 g / mL less than the density of the organic liquid containing malodorous components; Preferably, the density of the VOCs volatile inhibitor is 0.3 to 0.6 g / mL.
3. The VOCs volatilization inhibitor according to claim 1 or 2, characterized in that, The solvent is water.
4. The VOCs volatilization inhibitor according to any one of claims 1-3, characterized in that, The content of hollow microspheres is 3 to 20 parts by weight, preferably 6 to 15 parts by weight, relative to 100 parts by weight of the solvent. Preferably, the density of the hollow microspheres is 0.05–0.6 g / mL, more preferably 0.1–0.3 g / mL; Preferably, the median particle size D50 of the hollow microspheres is 5–500 μm, and more preferably 10–100 μm; Preferably, the hollow microspheres are made of soda lime borosilicate glass.
5. The VOCs volatilization inhibitor according to any one of claims 1-4, characterized in that, The content of the adsorbent material is 0.5 to 8 parts by weight, preferably 0.8 to 4 parts by weight, relative to 100 parts by weight of the solvent. Preferably, the adsorbent material is selected from activated carbon and / or metal-organic framework materials; More preferably, the specific surface area of the activated carbon is 800-2000 m². 2 / g, with an average pore size of 0.4–70 nm, a total pore volume of 0.5–1.6 mL / g, and a particle size of 10–500 μm; More preferably, the specific surface area of the metal-organic framework material is 600–1700 m². 2 / g, with an average pore size of 0.3–60 nm, a total pore volume of 0.6–2 mL / g, and a particle size of 10–500 μm.
6. The VOCs volatilization inhibitor according to any one of claims 1-5, characterized in that, The content of the surfactant is 0.01 to 6 parts by weight, preferably 0.03 to 2 parts by weight, relative to 100 parts by weight of the solvent. Preferably, the surfactant is a small molecule water-soluble surfactant with a molecular weight of 200 to 800 and / or a high molecular weight water-soluble surfactant with a molecular weight of 8,000 to 20,000. More preferably, the small molecule water-soluble surfactant is selected from at least one of sodium oleate, sodium laurylate, sodium stearate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, octadecylamine, cocoylamine, and dodecylamine; More preferably, the high molecular weight water-soluble surfactant is selected from at least one of polyacrylate and its derivatives, polyethyleneimine, polyvinylpyrrolidone, polyacrylamide and its derivatives, polyvinyl alcohol, polyoxyethylene polyoxypropylene ether, polyvinyl ether and fatty alcohol polyoxyethylene ether.
7. The VOCs evaporation inhibitor according to any one of claims 1-5, characterized in that, Based on the weight of the solvent, the content of the stabilizer is 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight; Preferably, the stabilizer is selected from cellulose compounds and / or starch; More preferably, the cellulose compound is selected from at least one of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, and hydroxypropylmethylcellulose.
8. The VOCs volatilization inhibitor according to any one of claims 1-7, characterized in that, The content of the dispersant is 0.1 to 6 parts by weight, preferably 0.5 to 3 parts by weight, relative to 100 parts by weight of the solvent. Preferably, the dispersant is a cationic dispersant and / or a polymeric dispersant; More preferably, the cationic dispersant is selected from at least one of amine salts, quaternary ammonium salts, and pyridinium salts; More preferably, the polymeric dispersant is selected from at least one of polycaprolactone polyol-polyethyleneimine block copolymer dispersants, polyacrylic acid dispersants, polyurethanes, and polyesters.
9. The VOCs evaporation inhibitor according to any one of claims 1-8, characterized in that, The content of the coupling agent relative to 100 parts by weight of the solvent is 0.05 to 8 parts by weight, preferably 0.2 to 4 parts by weight; Preferably, the coupling agent is selected from at least one of silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, and organic complexes.
10. The VOCs volatile inhibitor according to any one of claims 1-9, characterized in that, The VOCs volatile inhibitor also contains antibacterial agents and / or water-retaining agents.
11. The VOCs evaporation inhibitor according to claim 10, characterized in that, Based on the total weight of the VOCs volatile inhibitors, the content of the antibacterial agent is 0-1% by weight, preferably 0.04-0.2% by weight; Preferably, the antibacterial agent is selected from at least one of quaternary ammonium salt compounds, organohalides, and pyridine salt compounds.
12. The VOCs volatilization inhibitor according to claim 10 or 11, characterized in that, The water-retaining agent is selected from at least one of n-hexadecyl alcohol, n-octadecanol and n-butanol; Preferably, the thickness of the water-retaining agent above the liquid surface of the VOCs volatilization inhibitor is 3-4 mm.
13. The VOCs evaporation inhibitor according to any one of claims 1-12, characterized in that, The VOCs volatile inhibitor has a viscosity of <2000 cP, a conductivity of 1500–2500 PS / m, and an absolute value of 20–50 mV for its zeta potential.
14. The VOCs volatilization inhibitor according to any one of claims 1-13, characterized in that, The organic liquid containing malodorous components is a petroleum product, preferably light crude oil.
15. A method for suppressing the volatilization of organic liquids containing malodorous components, characterized in that, The method includes: delivering the VOCs volatile inhibitor according to any one of claims 1-14 above the surface of the organic liquid containing odorous components.