Method for simultaneously removing ash, reducing acid value and total sulfur of oil-containing pollutants of a ship

Abstract

The application discloses a method for simultaneously removing ash, reducing acid value and reducing total sediment of ship oil-containing pollutants, and belongs to the technical field of waste oil regeneration and utilization. The method aims to solve the problems of complex process and inability to simultaneously and efficiently remove various impurities in the prior art for treating ship oil-containing pollutants. The ship oil-containing pollutant raw material is heated to 75-85 DEG C, 5% of the raw material by mass of a composite treatment agent composed of polyoxypropylene polyoxyethylene ether block copolymer, triethanolamine, diethylene triamine and solvent oil is added, and constant temperature reaction is carried out for 1-2 hours; then 5% of the raw material by mass of water is added, and constant temperature reaction is continuously carried out for 1-2 hours; finally, the mixture is heated to 90-95 DEG C and then centrifugal separation is carried out, so that qualified marine fuel oil is obtained. The method has one-dose multi-effect and integrated process, and the process is simple; ash, acidic substances and total sediment in the raw material can be efficiently and synergistically removed; the product quality meets the national standard requirements; and the method has remarkable economic and environmental protection benefits.

Description

Technical Field

[0001] This invention relates to the field of waste oil recycling technology, and in particular to a treatment process for oily pollutants generated during ship operation, specifically a method that can simultaneously remove ash, reduce acid value and total precipitate in one process flow. Background Technology

[0002] Oily pollutants from ships, commonly referred to as "oil sludge" or "oil-water mixture," are oil-water mixtures generated during the operation, maintenance, and cleaning of ship engine rooms. Their sources are complex, typically including residual and leaked fuel oil, lubricating oil, and hydraulic oil, as well as mixed impurities such as water, seawater, coolant, catalyst powder (mainly alumina and silica), metal debris (rust), silt, gum, and asphaltene. Therefore, these pollutants are characterized by complex incoming material composition, high water content, high ash content, high acid value, and high total precipitate content.

[0003] According to the International Maritime Organization (IMO) Convention on the Prevention of Pollution from Ships (MARPOL 73 / 78), oily pollutants from ships are prohibited from being discharged into the ocean indiscriminately and must be properly collected and treated. Currently, the mainstream treatment method is to transport the pollutants to shore-based receiving facilities for centralized processing. Traditional treatment methods typically include simple physical separation (such as gravity settling and air flotation) and chemical treatment, but these methods have many drawbacks.

[0004] 1) Limited treatment effect: Traditional methods primarily aim at oil-water separation, but are inefficient at removing ash (metal compounds, catalyst powders, etc.) in the form of fine particles, soluble acidic substances, and asphaltenes that may form total precipitates. The treated product often still fails to meet the stringent requirements for key indicators such as ash content, acid value, and total precipitates in national standards for marine fuel oil (such as GB / T17411-2015).

[0005] 2) Complex process flow: In order to solve the problems of ash content, acid value and total sedimentation separately, existing technologies often require the use of multiple independent treatment units with significantly different process routes. For example, chemical demulsification and dehydration are performed first, followed by acid-base neutralization to reduce acid value, and finally, filtration or the addition of stabilizers may be required to control total sedimentation. This results in a lengthy treatment process, large equipment investment, high energy consumption and complex operation and management.

[0006] 3) Risk of secondary pollution: During the acid value reduction process, the use of strong acids or strong alkalis can easily lead to equipment corrosion, and if the generated salt substances are not handled properly, they can introduce new impurities or even produce waste liquid that is difficult to dispose of, causing secondary pollution.

[0007] Therefore, how to develop a process that is simple, low-cost, and highly efficient, and can simultaneously and efficiently solve the three major problems of ash, acid value, and total sediment in ship oil pollutants in a unified process, and convert them into marine fuel oil that meets the standards, is a technical problem that urgently needs to be solved in this field, and has significant economic value and environmental significance. Summary of the Invention

[0008] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for simultaneously removing ash, reducing acid value, and decreasing total sedimentation of oily pollutants from ships, which is simple in process, highly efficient in treatment, and low in energy consumption.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] A method for simultaneously removing ash, reducing acid value, and decreasing total sedimentation of oily pollutants from ships includes the following steps:

[0011] a. Heat the oily pollutant material from the ship to be treated to 75-85℃;

[0012] b. While stirring, add 5% (by weight of the raw material) of a composite treatment agent to the heated raw material, and react at a constant temperature of 75-85°C for 1-2 hours; the composite treatment agent comprises the following components:

[0013] Component A: A nonionic surfactant used as a demulsifier and wetting agent;

[0014] Component B: Organic amine compounds that act as acid value neutralizers and chelating agents;

[0015] Component C: Polyamine compound used as a flocculant;

[0016] Component D: Solvent oil as the dispersion medium;

[0017] c. After completing the reaction in step b, continue to add water at 5% of the mass of the raw material while stirring, and continue to react at a constant temperature of 75-85°C for 1-2 hours to extract the reaction products and impurities;

[0018] d. The mixture obtained after step c is subjected to three-phase separation by a centrifugal separator to obtain marine fuel oil product as the light phase, wastewater as the heavy phase, and impurities as the solid phase. The ash content, acid value, and total precipitate of the marine fuel oil product are reduced.

[0019] As a further optimization of the present invention, component A in the composite treatment agent is a polyoxypropylene polyoxyethylene ether block copolymer; component B is triethanolamine; component C is diethylenetriamine; and component D is heavy aromatic solvent oil.

[0020] As a further optimization of the present invention, the composite treatment agent is composed of the following components by mass percentage:

[0021] Polyoxypropylene polyoxyethylene ether block copolymer: 15-25%;

[0022] Triethanolamine: 25-40%;

[0023] Diethylenetriamine: 5-15%;

[0024] Heavy aromatic solvent oil: balance.

[0025] As a further optimization of the present invention, the composite treatment agent is composed of the following components by mass percentage:

[0026] Polyoxypropylene polyoxyethylene ether block copolymer: 20%;

[0027] Triethanolamine: 35%;

[0028] Diethylenetriamine: 10%;

[0029] Heavy aromatic solvent oil: 35%.

[0030] As a further optimization of the present invention, the heating in steps a and b is achieved by the jacket steam of the reactor, and the temperature of the jacket steam is controlled at 105-115°C.

[0031] As a further optimization of the present invention, the stirring speed in steps b and c is controlled at 200-500 rpm.

[0032] As a further optimization of the present invention, before performing the centrifugation separation in step d, the method further includes a step of raising or maintaining the temperature of the mixture at 90-95°C.

[0033] As a further optimization of the present invention, the marine fuel oil product obtained in step d has quality indicators that meet or exceed the requirements of RME180 marine residual fuel oil in GB / T17411 standard.

[0034] This invention also provides a composite treatment agent for deashing, deacidifying, and reducing total precipitates of oily pollutants in ships, comprising the following components by mass percentage:

[0035] Polyoxypropylene-polyoxyethylene ether block copolymer as a demulsifier and wetting agent: 15-25%;

[0036] Triethanolamine as an acid value neutralizer and chelating agent: 25-40%;

[0037] Diethylenetriamine as a flocculant: 5-15%;

[0038] Heavy aromatic solvent oil as dispersion medium: balance.

[0039] As a further optimization of the present invention, it is composed of the following components by mass percentage:

[0040] Polyoxypropylene polyoxyethylene ether block copolymer: 20%;

[0041] Triethanolamine: 35%;

[0042] Diethylenetriamine: 10%;

[0043] Heavy aromatic solvent oil: 35%.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0045] 1) One agent with multiple effects and synergistic treatment: This invention proposes a composite treatment agent in which the components in the formula complement each other and synergistically enhance each other. Under the same process conditions, it can simultaneously achieve four major functions: demulsification, neutralization, chelation and flocculation, and solve three major problems of ash, acid value and total precipitate in one go, avoiding the complicated process of multiple treatment systems and multiple dosing.

[0046] 2) Simplified process and convenient operation: This invention simplifies the complex process into four core steps: "heating-dosage reaction-water reaction-centrifugation separation". All the main reactions are completed in the same reactor. The process is short, easy to control, and greatly reduces equipment investment and operation difficulty.

[0047] 3) Significant treatment effect and high product quality: Through the close combination of chemical reaction and physical separation, this invention can efficiently process unqualified ship oily pollutant raw materials into products that meet the GB / T17411 RME180 marine fuel oil standard, with high resource utilization rate and corresponding increase in product added value.

[0048] 4) Green and environmentally friendly with good economic benefits: This invention uses mild organic amines instead of strong acids and alkalis, avoiding equipment corrosion and secondary pollution. The entire process has low energy consumption and controllable processing costs, transforming waste into valuable commodities and achieving a balance between environmental and economic benefits. Attached Figure Description

[0049] Figure 1 This is a schematic diagram of the process flow according to an embodiment of the present invention. Detailed Implementation

[0050] The present invention will now be described in further detail with reference to the accompanying drawings. The embodiments described with reference to the drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

[0051] The main equipment used in this invention refers to the "pilot plant for sludge and oil regeneration unit" in the technical disclosure document, including but not limited to:

[0052] Reactor: Reactor No. 1, model ∅90032006 / 600L / Q345R, equipped with steam heating jacket and mechanical stirring device.

[0053] Centrifuge: Model GF-125 three-phase tubular centrifuge with a processing capacity of approximately 150L / h.

[0054] Transfer pump: Gear pump, used for transferring oil products.

[0055] Storage tanks: raw material transfer tanks, semi-finished product transfer tanks, finished product tanks, etc.

[0056] Example 1

[0057] This embodiment aims to illustrate the basic process flow of the present invention.

[0058] A method for simultaneously removing ash, reducing acid value, and decreasing total sedimentation of oily pollutants from ships includes the following specific steps:

[0059] (1) Raw material preparation and feeding:

[0060] A batch of ships carrying oil pollutants was received from a port. Testing revealed the following key indicators:

[0061] Appearance: Dark brown viscous liquid with an oily odor

[0062] Moisture content (V / V): 4.8%

[0063] Ash content (m / m): 1.52%

[0064] Acid value: 4.1 mgKOH / g

[0065] Total precipitate (m / m): 0.85%

[0066] Density (20℃): 945 kg /

[0067] Clearly, the ash content, acid value, and total precipitate of this raw material far exceed the standards for marine fuel oil.

[0068] Use a gear pump to pump 350L (approximately 330kg) of the raw material into a 600L reactor.

[0069] (2) Heating and the primary reaction:

[0070] Close all non-essential valves in the reactor, open the jacket steam inlet valve and drain valve, and set the jacket steam temperature to 110℃. Simultaneously start the reactor's agitator and set the speed to 300 rpm. Heat the material inside the reactor from room temperature to 80℃.

[0071] Once the temperature reaches 80℃, slowly add 16.5 kg (330 kg * 5%) of the composite treatment agent into the reactor through the dosing port. The formulation (by mass percentage) of this agent is: 20% polyoxypropylene polyoxyethylene ether block copolymer, 35% triethanolamine, 10% diethylenetriamine, and 35% heavy aromatic solvent oil.

[0072] After adding the reagent, maintain the temperature inside the reactor at 80℃ for 1.5 hours.

[0073] (3) Secondary reaction upon addition of water:

[0074] After one reaction cycle, while maintaining constant stirring and temperature, 16.5 kg (330 kg * 5%) of industrial tap water was added to the reactor using a metering pump. After the water was added, the reaction was continued at a constant temperature of 80°C with stirring for 1.5 hours. During this process, the mixture was observed to change from a homogeneous oily state to a slightly stratified liquid.

[0075] (4) Centrifugal separation:

[0076] After the secondary reaction is complete, stop stirring. Open the steam valve to raise the temperature of the mixture in the reactor to 95°C and maintain this temperature.

[0077] Start the GF-125 tubular centrifuge and, once it reaches full speed, pump the hot mixture in the reactor into the centrifuge at a flow rate of 150 L / h using a transfer pump.

[0078] The centrifuge separated three streams of material:

[0079] Light phase: Purified marine fuel oil semi-finished product, collected in semi-finished product transfer tank.

[0080] Heavy phase: wastewater containing salts produced in the reaction and captured impurities.

[0081] Solid phase: Waste residue, mainly consisting of high concentrations of ash, colloids, etc., deposited on the centrifuge drum wall, which needs to be cleaned regularly.

[0082] (5) Results Analysis:

[0083] The collected semi-finished marine fuel oil was sampled and tested, and its main indicators are as follows:

[0084] Moisture content (V / V): 0.4%

[0085] Ash content (m / m): 0.06%

[0086] Acid value: 2.2 mgKOH / g

[0087] Total precipitate (m / m): 0.08%

[0088] Density (20℃): 978 kg /

[0089] Kinematic viscosity (50℃): 175 / s

[0090] Comparing the data before and after the treatment, it can be seen that, after the process of this embodiment, all the indicators of the product have met the quality standards of RME180 marine residual fuel oil in GB / T17411-2015. Ash, acid value and total precipitate are removed simultaneously and efficiently.

[0091] Example 2

[0092] This embodiment aims to illustrate the processing effects under different process parameters.

[0093] Another batch of oily pollutants from ships was treated, with initial parameters of 1.85% ash, 3.8 mgKOH / g acid value, and 0.65% total precipitate. The treatment capacity was 350L.

[0094] The process steps are basically the same as in Example 1, but some parameters have been adjusted:

[0095] (1) Heating and primary reaction: The raw materials were heated to 75°C. After adding 5% of the composite treatment agent by mass of the raw materials, the reaction was carried out at 75°C for 2 hours. The stirring rate was 400 rpm.

[0096] The formulation (by mass percentage) of the composite treatment agent used in this embodiment is as follows: 15% polyoxypropylene polyoxyethylene ether block copolymer, 40% triethanolamine, 15% diethylenetriamine, and 30% heavy aromatic solvent oil.

[0097] (2) Secondary reaction with water: After the first reaction is completed, add water at 5% of the mass of the raw material and continue the reaction at 75°C for 2 hours.

[0098] (3) Centrifugal separation: Before separation, the mixture is heated to 90°C and then centrifuged.

[0099] (4) Results Analysis:

[0100] The main indicators of the semi-finished fuel oil obtained after processing are as follows:

[0101] Ash content (m / m): 0.07%

[0102] Acid value: 2.4 mgKOH / g

[0103] Total precipitate (m / m): 0.09%

[0104] The results show that even at lower reaction temperatures and longer reaction times, and with the use of reagents with adjusted formulations, the process of the present invention can still effectively remove various impurities and ensure that the product meets the standards, demonstrating that the process of the present invention has a wide process parameter window and good adaptability.

[0105] Example 3

[0106] This example is intended to illustrate the effects of treatment at higher reaction temperatures.

[0107] A batch of oily pollutants from ships with exceptionally high acid values ​​was treated. The initial parameters were: ash content 1.25%, acid value 5.5 mg KOH / g, and total precipitate 0.70%. The treatment capacity was 350 L.

[0108] The process steps are basically the same as in Example 1, but some parameters have been adjusted:

[0109] (1) Heating and primary reaction: The raw materials were heated to 85°C. After adding 5% of the composite treatment agent by mass of the raw materials, the reaction was carried out at 85°C for 1 hour. The stirring rate was 500 rpm.

[0110] The formulation (by mass percentage) of the composite treatment agent used in this embodiment is as follows: 25% polyoxypropylene polyoxyethylene ether block copolymer, 30% triethanolamine, 5% diethylenetriamine, and 40% heavy aromatic solvent oil.

[0111] (2) Secondary reaction with water: After the first reaction is completed, add water at 5% of the mass of the raw material and continue the reaction at 85°C for 1 hour.

[0112] (3) Centrifugal separation: Before separation, the mixture is heated to 95°C and then centrifuged.

[0113] (4) Results Analysis:

[0114] The main indicators of the semi-finished fuel oil obtained after processing are as follows:

[0115] Ash content (m / m): 0.05%

[0116] Acid value: 2.5 mgKOH / g

[0117] Total precipitate (m / m): 0.07%

[0118] The results show that for raw materials with particularly high acid values, by increasing the reaction temperature and stirring intensity, and adjusting the reagent formulation, the treatment can be completed in a shorter time, and the treatment effect is still very ideal. This proves that the process of the present invention has a strong ability to treat inferior raw materials with different properties.

[0119] In summary, this invention provides an innovative, efficient, and integrated technology for treating oily pollutants from ships. By using a specially formulated composite chemical agent combined with an optimized process, it successfully solves the technical challenges of simultaneously removing ash, reducing acid value, and decreasing total precipitate. This technology demonstrates significant advancement and practicality, and has broad market application prospects.

[0120] The above descriptions are merely some embodiments of the present invention. Those skilled in the art can make various modifications and improvements without departing from the inventive concept of the present invention, and these all fall within the scope of protection of the present invention.

Claims

1. A method for simultaneously removing ash, reducing acid value, and decreasing total sedimentation of oily pollutants from ships, characterized in that, Includes the following steps: a. Heat the oily pollutant material from the ship to be treated to 75-85℃; b. While stirring, add 5% (by weight of the raw material) of a composite treatment agent to the heated raw material, and react at a constant temperature of 75-85°C for 1-2 hours; the composite treatment agent comprises the following components: Component A: A nonionic surfactant used as a demulsifier and wetting agent; Component B: Organic amine compounds that act as acid value neutralizers and chelating agents; Component C: Polyamine compound used as a flocculant; Component D: Solvent oil as the dispersion medium; c. After completing the reaction in step b, continue to add water at 5% of the mass of the raw material while stirring, and continue to react at a constant temperature of 75-85°C for 1-2 hours to extract the reaction products and impurities; d. The mixture obtained after step c is subjected to three-phase separation using a centrifugal separator to obtain marine fuel oil product as the light phase, wastewater as the heavy phase, and impurities as the solid phase. The ash content, acid value, and total precipitate of the marine fuel oil product are reduced. In the composite treatment agent, component A is a polyoxypropylene-polyoxyethylene ether block copolymer; component B is triethanolamine; component C is diethylenetriamine; and component D is a heavy aromatic solvent oil. The composite treatment agent consists of the following components by mass percentage: Polyoxypropylene polyoxyethylene ether block copolymer: 15-25%; Triethanolamine: 25-40%; Diethylenetriamine: 5-15%; Heavy aromatic solvent oil: balance. Before performing the centrifugation separation in step d, the process also includes raising or maintaining the temperature of the mixture at 90-95°C.

2. The method according to claim 1, characterized in that, The composite treatment agent consists of the following components by mass percentage: Polyoxypropylene polyoxyethylene ether block copolymer: 20%; Triethanolamine: 35%; Diethylenetriamine: 10%; Heavy aromatic solvent oil: 35%.

3. The method according to claim 1, characterized in that, The heating in steps a and b is achieved by steam in the jacket of the reactor, and the temperature of the steam in the jacket is controlled at 105-115℃.

4. The method according to claim 1, characterized in that, The stirring speed in steps b and c is controlled at 200-500 rpm.

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