WO2023185249A1 - New method for preparing carbon-based shaped engine oil purification material for vehicles and ships - Google Patents

New method for preparing carbon-based shaped engine oil purification material for vehicles and ships Download PDF

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WO2023185249A1
WO2023185249A1 PCT/CN2023/074302 CN2023074302W WO2023185249A1 WO 2023185249 A1 WO2023185249 A1 WO 2023185249A1 CN 2023074302 W CN2023074302 W CN 2023074302W WO 2023185249 A1 WO2023185249 A1 WO 2023185249A1
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engine oil
vehicles
ships
carbon
temperature
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PCT/CN2023/074302
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French (fr)
Chinese (zh)
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卢辛成
孙康
蒋剑春
赵剑
卫民
徐茹婷
张燕萍
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中国林业科学研究院林产化学工业研究所
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Publication of WO2023185249A1 publication Critical patent/WO2023185249A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2055—Carbonaceous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration

Definitions

  • the invention belongs to the technical fields of activated carbon material application and engine oil filtration, and specifically relates to a new method for preparing carbon-based shaped engine oil purification materials for vehicles and ships.
  • engine oil needs to be continuously transported to the surface of various engine components to form a lubricating oil film, which reduces the frictional resistance of various parts of the engine during operation, reduces parts wear, lowers engine temperature, and improves engine operating efficiency and gasoline utilization efficiency. , thereby ensuring stable and efficient operation of the engine.
  • metal wear debris, carbon deposits, and dust in the air are produced during operation and mixed into the engine oil, increasing the impurity content of the engine oil.
  • the engine generates high-temperature and high-pressure environments during operation, causing the engine oil to be oxidized. , decompose to form colloid and other substances, reducing the quality of engine oil.
  • the increased impurity content and reduced quality of engine oil are not conducive to the stable operation and work of the engine. Therefore, it is necessary to use an oil filter to filter oil impurities and improve oil quality to ensure efficient and stable operation of the engine.
  • the filter element is the main component of the oil filter. Its function is to filter impurities such as dust, metal scraps, carbon deposits, and colloidal sediments generated during the operation of the engine, thereby keeping the engine oil clean and extending the service life of the engine oil; at the same time , clean engine oil helps reduce friction during engine operation, lower engine temperature, prevent engine early ignition and deflagration, increase engine effective power, improve gasoline combustion efficiency, save fuel and consumption, and reduce exhaust pollution emissions.
  • a high-quality oil filter element needs to have good dirt holding capacity and purification effect. It also needs to have good high temperature resistance and pressure resistance under high temperature environment and large flux flow rate of oil.
  • Activated carbon material has rich pore structure, stable physical and chemical properties and excellent adsorption performance, and is an excellent material for preparing filter elements. By further adding adhesives, it can be prepared through cementation molding to obtain filter element devices of different shapes, which can be adapted to filters of different car models and are easy to use. Automated and large-scale production. However, due to the complex composition of engine oil and the production of various impurities during use, its removal mechanism is significantly different from that in traditional water phases.
  • Carbonaceous adsorption materials with specific pore structure distribution, composition and surface chemical characteristics are needed to enhance adsorption and improve dirt holding capacity. quantity to improve the purification performance of engine oil.
  • the binder used not only needs to have good oil resistance, high temperature resistance and cementing strength, but also needs to maintain good adsorption and purification effects without blocking the pore structure of the adsorbent material itself when forming the gel.
  • ordinary activated carbon materials are used for engine oil purification, their surface microstructure is not suitable for the adsorption and removal of oil phase impurities. There are problems such as low purification efficiency, small dirt holding capacity, and short service life.
  • a technical problem to be solved by the present invention is to provide a carbon-based shaped engine oil purification material for vehicles and ships.
  • a new preparation method is used to prepare carbon-based shaped oil purification materials with a special network structure for automobiles and ships to be used as oil purification filters through structural regulation of carbonaceous adsorption materials, adhesive modification and controllable coupling of material processes.
  • Another technical problem to be solved by the present invention is to provide a carbon-based shaping purification material for vehicles and ships.
  • This purification material has a unique mesh structure, is resistant to high temperatures, is resistant to oil, and can adapt to large flux flow rates of engine oil. Its mesh-channel structure The filtration effect and the adsorption effect of the adsorption material make it have a large dirt holding capacity and good purification performance. It also has the advantages of controllable molding and wide adaptability, and is easy to automate and large-scale production.
  • a new method for preparing carbon-based molding oil purification materials for vehicles and ships Carbon adsorbent materials with special microstructures and polymer adhesives are uniformly mixed in a certain ratio and solidified to form carbon-based molding materials with a unique network structure for vehicles and ships. Oil purification materials.
  • This unique mesh structure is a mesh-channel-pore structure, which has the filtration effect of the mesh-channel and the adsorption effect of the pore structure. It has good purification performance, high dirt holding capacity, and is suitable for large-flow oil filtration needs of vehicles and ships.
  • the new method for preparing carbon-based stereotyped engine oil purification materials for vehicles and ships is granular activated carbon that has been controlled to be mainly micro- and mesopores. Its pore structure distribution ratio is microporosity ⁇ 30% and mesopores 30%. ⁇ 70%; preferably the microporosity is 21% to 30% and the mesoporosity is 44% to 66%.
  • the new method for preparing carbon-based stereotyped engine oil purification materials for vehicles and ships is an activated carbon material whose surface is controlled to contain rich nitrogen and oxygen functional groups.
  • the content of nitrogen-containing functional groups is 2% to 15%, and the content of oxygen-containing functional groups is 1 to 6 mmol/g, pH value is 8 to 14; preferably, the content of nitrogen-containing functional groups is 5.27%-13.43%, the content of oxygen-containing functional groups is 2.05-3.85 mmol/g, and the pH value is 8.3-12.5.
  • the polymer adhesive is prepared by adding reaction aids to the main body of the resin glue. It is oil-resistant and high-temperature resistant and can form an open-pore permeable adhesive film through controllable cementation.
  • the main body of the resin glue is a mixture of two or more of polyester polyurethane, polyether polyurethane, phenolic resin, urea-formaldehyde resin, epoxy resin, toluene diisocyanate or diphenylmethane diisocyanate, and the reaction aid is One or a mixture of one or more of diethylamine, triethanolamine, diethylenediamine, acetamide or polyacrylamide.
  • the new method for preparing carbon-based shaped engine oil purification materials for vehicles and ships is: controllable cementation and pressure molding at normal temperature, solidification at low temperature, and maturation at high temperature.
  • the specific steps are: at normal temperature, the carbonaceous adsorption material and the polymer adhesive are uniformly mixed and controllably cemented in a mass ratio of 1:1 to 10:1, and then loaded into the mold and pressurized for molding.
  • the molding pressure is 0.1 to 10:1. 2.0kg/cm 2 , time is 10-30min; then placed in a temperature-controlled container for curing at low temperature, curing temperature is 40-100°C, time is 20-90min; and then further cured at high temperature, curing temperature is 100-300 °C, time is 30 ⁇ 200min.
  • the curing temperature is 40-85°C and the time is 30-90 minutes; the aging temperature is 120-280°C and the time is 50-180 minutes.
  • the new method for preparing carbon-based shaping engine oil purification materials for vehicles and ships includes the following steps:
  • step (3) Add the polymer adhesive prepared in step (2) to the carbonaceous adsorption material adjusted in step (1), mix it evenly at room temperature, controllably cement it and fill it in a fixed mold, and then press and mold it.
  • the mold is placed in a temperature-controlled container for low-temperature solidification. After solidification, it is taken out and cooled to room temperature for demoulding. The mold is then further matured at high temperature to obtain a carbon-based shaping engine oil purification material.
  • the carbon-based shaped engine oil purification material for vehicles and ships is prepared by the above method.
  • the present invention improves the sensitivity of different molecules and particles by regulating the pore structure distribution and composition of the carbonaceous adsorption materials.
  • the physical adsorption of large and small impurities achieves hierarchical adsorption; at the same time, the content of oxygen-containing and nitrogen-containing functional groups and pH value on its surface are controlled to enhance its chemical adsorption of impurities through complexation.
  • the regulation and modification of the microstructure and surface properties of carbon-based adsorption materials make them more suitable for the removal of impurities in engine oil, increase the adsorption capacity of impurities and dirt holding capacity, and improve the purification effect.
  • the body-structured polymer adhesive formed by the molecular chain reaction of polymer resin glue in the present invention does not dissolve, melt or swell in high-temperature engine oil, and has good oil resistance, high temperature resistance and cementing strength, forming
  • the open-pore permeable adhesive film ensures good bonding strength while not blocking the original pore structure of the carbonaceous adsorption material, thereby maintaining excellent adsorption performance.
  • the carbon-based shaped engine oil purification material for vehicles and ships of the present invention has a unique mesh structure, has the filtering effect of the mesh-channel structure and the adsorption effect of the activated carbon pores, has high dirt holding capacity, good purification performance, and is suitable for large-flow engine oil in vehicles and ships. Filtration requirements, it also has the advantages of oil resistance, high temperature resistance, controllable molding, wide adaptability, etc., and is easy to automate and large-scale production.
  • Figure 1 is a diagram of the carbon-based shaped oil purification material and its mesh-channel-pore structure.
  • the oxygen-containing functional groups disclosed in the present invention are mainly phenolic hydroxyl groups, carboxyl groups and carbonyl groups, and the nitrogen-containing functional groups are mainly pyrrole, pyridine and nitrogen-oxygen types.
  • the contents of oxygen-containing functional groups and nitrogen-containing functional groups are measured by Bothem titration and XPS respectively.
  • a new method for preparing carbon-based styling engine oil purification materials for vehicles and ships including the following steps:
  • the microporosity and mesoporosity of activated carbon materials are controlled to 29.37% and 29.37%, respectively. 44.67%, the surface oxygen-containing functional group content is 2.07mmol/g, the nitrogen-containing functional group content is 13.43%, and the pH value is 12.5;
  • the main body of the resin glue is polyether polyurethane, phenolic resin and toluene diisocyanate in a mass ratio of 2:2:1, and then the reaction aid triethanolamine is added in a mass ratio of 10:1 to make a polymer adhesive;
  • a new method for preparing carbon-based styling engine oil purification materials for vehicles and ships including the following steps:
  • the activated carbon material has a microporosity of 25.21%, a mesoporosity of 58.38%, a surface oxygen-containing functional group content of 2.05mmol/g, and a nitrogen-containing functional group content of 5.27%. pH value 8.3;
  • the main body of the resin glue is compounded with phenolic resin and urea-formaldehyde resin at a mass ratio of 1:1, and then the reaction aid polyacrylamide is added at a mass ratio of 8:1 to make a polymer adhesive;
  • a new method for preparing carbon-based styling engine oil purification materials for vehicles and ships including the following steps:
  • the microporosity of the activated carbon material is 21.17%, the mesoporosity is 65.73%, the surface oxygen-containing functional groups are 3.03 mmol/g, the nitrogen-containing functional groups are 12.64%, and the pH value is 11.3;
  • the main body of the resin glue is compounded with phenolic resin and urea-formaldehyde resin at a mass ratio of 1.5:1, and then the reaction aid polyacrylamide is added at a mass ratio of 10:1 to make a polymer adhesive;
  • a new method for preparing carbon-based styling engine oil purification materials for vehicles and ships including the following steps:
  • the microporosity of the activated carbon material is 21.17%, the mesoporosity is 65.73%, the surface oxygen-containing functional groups are 3.03 mmol/g, the nitrogen-containing functional groups are 12.64%, and the pH value is 11.3;
  • the main body of the resin glue is polyester polyurethane, epoxy resin, urea-formaldehyde resin and toluene diisocyanate, which are compounded in a mass ratio of 1:1:1:1, and then the reaction aid diethyl is added in a mass ratio of 15:1.
  • Amine made into polymer adhesive;
  • the preparation method of carbon-based styling and purification materials for vehicles and ships includes the following steps:
  • the activated carbon material has a microporosity of 24.21%, a mesoporosity of 58.36%, a surface oxygen-containing functional group of 3.85 mmol/g, a nitrogen-containing functional group of 10.57%, and a pH value of 9.7;
  • the main body of the resin glue is compounded with polyether polyurethane, phenolic resin and diphenylmethane diisocyanate in a mass ratio of 1:1:1, and then the reaction aid acetamide is added in a mass ratio of 25:1 to make polymer adhesive;
  • Example 4 The difference from Example 4 is that the activated carbon used has a microporosity of >60%, a surface oxygen-containing functional group content of 1.05 mmol/g, no nitrogen-containing functional groups, and a pH of 7.2.
  • Example 4 The difference from Example 4 is that the polymer adhesive used is a single resin, urea-formaldehyde resin, and is not compounded.
  • Example 4 The difference from Example 4 is that no reaction aid is added to the polymer adhesive used.
  • Examples 1-5 and Comparative Examples 1-3 are as follows: using colloid (n-pentane insoluble matter) 1.97%, iron content 83.47mg/Kg, copper content 43.15mg/Kg, aluminum content 36.21 mg/Kg, the engine oil with an acid value of 3.4mg/g is crude oil, refer to GB/T8028, carry out experiments and index tests at 100°C, use the GB/T8926 method to measure the colloid (insoluble matter) in the engine oil, and calculate the colloid removal rate ; Use GB/T17476 inductively coupled plasma emission spectrometry to determine the iron, copper, and aluminum content in engine oil, and calculate the removal rate and adsorption capacity; use GB/T 7304 to determine the acid value of engine oil.
  • Table 1 The test results are shown in Table 1 below:
  • Examples 1 to 5 of the present invention show higher performance in high-temperature oil purification. It has adsorption capacity, larger dirt holding capacity and more significant purification effect. It has good oil resistance and high temperature resistance, and is more suitable for filtration and purification of high temperature engine oil.
  • Figure 1 shows carbon-based styling oil purification materials.
  • a is the mesh structure of the carbon-based shaped oil purification material
  • b is the rich channel structure formed between the activated carbon particles in the carbon-based shaped oil purification material
  • c is the openings formed on the surface of the activated carbon in the carbon-based shaped oil purification material type permeable membrane, which does not block the original pore structure of activated carbon materials and maintains its excellent adsorption performance.

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  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Disclosed in the present invention is a new method for preparing a carbon-based shaped engine oil purification material for vehicles and ships, which belongs to the technical fields of application of activated carbon materials and engine oil filtration. The method comprises: mixing a carbonaceous adsorption material having a special microstructure with a macromolecular adhesive at a certain ratio until uniform, and curing and forming same to prepare a carbon-based shaped engine oil purification material having a unique net-shaped structure for vehicles and ships. By regulating and controlling the microstructure and surface characteristics of the carbonaceous adsorption material, the purification material is more suitable for removing impurities in engine oil, and the dirt containing capacity and purification effect thereof are improved. By means of a molecular chain reaction of a resin adhesive, a polymer adhesive having a three-dimensional structure is formed, such that the oil resistance, the high-temperature resistance and the bonding strength are improved, and an open-cell type permeable adhesive film is formed and does not block the original pore structure of the adsorption material, thereby maintaining a good adsorption performance. By means of the coupling of the materials and the process, a unique net-shaped structure is formed; therefore, the purification material adapts to the large-throughput flow velocity of engine oil for vehicles and ships, the filtering effect of a woven net-channel structure and the adsorption effect of pore channels of the carbonaceous adsorption material are given to play, and the performance of purifying engine oil is improved.

Description

一种车船用碳基定型机油净化材料制备新方法A new method for preparing carbon-based shaped engine oil purification materials for vehicles and ships 技术领域Technical field
本发明属于活性炭材料应用及机油过滤技术领域，具体涉及一种车船用碳基定型机油净化材料制备新方法。The invention belongs to the technical fields of activated carbon material application and engine oil filtration, and specifically relates to a new method for preparing carbon-based shaped engine oil purification materials for vehicles and ships.
背景技术Background technique
在发动机运行过程中，机油需要被不断输送到发动机各个部件表面，形成润滑油膜，减少发动机在运行过程中各机件的摩擦阻力、减轻零件磨损、降低发动机温度，提高发动机运行效率和汽油利用效率，进而保证发动机稳定高效运行。随着发动机不断运行，在工作过程中产生金属磨屑、积碳以及空气中的粉尘等混入机油中，使机油杂质含量增加；同时，发动机在运行过程中产生高温和高压环境，使机油被氧化、分解形成胶质和其他物质，降低机油品质。机油杂质含量增加和品质降低，不利于发动机稳定运行和工作。因此，需要通过机油滤清器过滤机油杂质、改善机油品质，进而保证发动机高效稳定运行。During engine operation, engine oil needs to be continuously transported to the surface of various engine components to form a lubricating oil film, which reduces the frictional resistance of various parts of the engine during operation, reduces parts wear, lowers engine temperature, and improves engine operating efficiency and gasoline utilization efficiency. , thereby ensuring stable and efficient operation of the engine. As the engine continues to run, metal wear debris, carbon deposits, and dust in the air are produced during operation and mixed into the engine oil, increasing the impurity content of the engine oil. At the same time, the engine generates high-temperature and high-pressure environments during operation, causing the engine oil to be oxidized. , decompose to form colloid and other substances, reducing the quality of engine oil. The increased impurity content and reduced quality of engine oil are not conducive to the stable operation and work of the engine. Therefore, it is necessary to use an oil filter to filter oil impurities and improve oil quality to ensure efficient and stable operation of the engine.
滤芯是机油滤清器发挥作用的主要部件，其作用是过滤发动机在工作过程中产生的尘土、金属磨屑、积碳以及胶状沉淀物等杂质，进而保持机油清洁，延长机油使用寿命；同时，清洁机油有助于减少发动机工作中摩擦、降低发动机温度，防止发动机早燃、爆燃现象，提高发动机有效功率，提升汽油燃烧效率，节油降耗、减少排气污染排放。The filter element is the main component of the oil filter. Its function is to filter impurities such as dust, metal scraps, carbon deposits, and colloidal sediments generated during the operation of the engine, thereby keeping the engine oil clean and extending the service life of the engine oil; at the same time , clean engine oil helps reduce friction during engine operation, lower engine temperature, prevent engine early ignition and deflagration, increase engine effective power, improve gasoline combustion efficiency, save fuel and consumption, and reduce exhaust pollution emissions.
优质的机油滤芯需要具备良好容污量和净化效果，同时还需要具有满足机油高温环境、大通量流速条件下良好的耐高温和耐压性。活性炭材料具有丰富的孔隙结构、稳定的理化性质和优良的吸附性能，是制备滤芯的优良材料；进一步添加胶黏剂通过胶结成型制备得到不同形状滤芯器件，适配不同车型滤清器，且易于自动化、规模化生产。但是由于机油成分复杂并且在使用过程产生多种杂质，因此其去除机制与传统水相中显著不同，需要特定孔结构分布、组成以及表面化学特性的碳质吸附材料，增强吸附作用、提高容污量，提升对机油的净化性能。同时，对于所用粘结剂来说，不仅需要具备良好的耐油、耐高温和胶结强度，还需要成胶时不堵塞吸附材料自身孔结构而保持良好吸附作用与净化效果。目前，普通的活性炭材料在用于机油净化时，其表面微结构不适应于油相杂质吸附去除，存在净化效率低、容污量小、使用寿命短等问题，同时常规胶黏剂均为线性结构、低温固化，胶结时其耐温性差、胶结强度低并且形成致密胶膜堵塞吸附材料孔道而使其吸附作用显著降低，进而导致制备的碳基滤芯整体机油耐温性差、净化性能低、使用寿命短，难以满足车船用大流量机油高效过滤要求。 A high-quality oil filter element needs to have good dirt holding capacity and purification effect. It also needs to have good high temperature resistance and pressure resistance under high temperature environment and large flux flow rate of oil. Activated carbon material has rich pore structure, stable physical and chemical properties and excellent adsorption performance, and is an excellent material for preparing filter elements. By further adding adhesives, it can be prepared through cementation molding to obtain filter element devices of different shapes, which can be adapted to filters of different car models and are easy to use. Automated and large-scale production. However, due to the complex composition of engine oil and the production of various impurities during use, its removal mechanism is significantly different from that in traditional water phases. Carbonaceous adsorption materials with specific pore structure distribution, composition and surface chemical characteristics are needed to enhance adsorption and improve dirt holding capacity. quantity to improve the purification performance of engine oil. At the same time, the binder used not only needs to have good oil resistance, high temperature resistance and cementing strength, but also needs to maintain good adsorption and purification effects without blocking the pore structure of the adsorbent material itself when forming the gel. At present, when ordinary activated carbon materials are used for engine oil purification, their surface microstructure is not suitable for the adsorption and removal of oil phase impurities. There are problems such as low purification efficiency, small dirt holding capacity, and short service life. At the same time, conventional adhesives are all linear structure, low-temperature curing, poor temperature resistance, low cementation strength during cementation, and the formation of a dense film that blocks the pores of the adsorbent material and significantly reduces its adsorption effect, which in turn results in the prepared carbon-based filter element having poor overall engine oil temperature resistance, low purification performance, and poor use The service life is short and it is difficult to meet the high-efficiency filtration requirements of large-flow engine oil used in automobiles and ships.
发明内容Contents of the invention
针对现有碳基机油净化滤芯存在的容污量小、净化效率低、耐温性差、胶膜堵孔等问题，本发明要解决的一个技术问题在于提供一种车船用碳基定型机油净化材料制备新方法，通过碳质吸附材料结构调控、胶黏剂改性及材料工艺可控耦合，制备具有特殊网状结构的车船用碳基定型机油净化材料用作机油净化滤芯。本发明要解决的另一个技术问题在于提供一种车船用碳基定型净化材料，该净化材料具有独特网状结构、耐高温、耐油、能适应机油大通量流速，其网状-通道结构的过滤作用与吸附材料的吸附作用使其容污量大、净化性能好，同时具备成型可控、适应性广等优点，易于自动化、规模化生产。In view of the problems existing in the existing carbon-based oil purification filter elements such as small dirt holding capacity, low purification efficiency, poor temperature resistance, and blocked holes in the film, a technical problem to be solved by the present invention is to provide a carbon-based shaped engine oil purification material for vehicles and ships. A new preparation method is used to prepare carbon-based shaped oil purification materials with a special network structure for automobiles and ships to be used as oil purification filters through structural regulation of carbonaceous adsorption materials, adhesive modification and controllable coupling of material processes. Another technical problem to be solved by the present invention is to provide a carbon-based shaping purification material for vehicles and ships. This purification material has a unique mesh structure, is resistant to high temperatures, is resistant to oil, and can adapt to large flux flow rates of engine oil. Its mesh-channel structure The filtration effect and the adsorption effect of the adsorption material make it have a large dirt holding capacity and good purification performance. It also has the advantages of controllable molding and wide adaptability, and is easy to automate and large-scale production.
为了解决上述问题，本发明所采用的技术方案如下：In order to solve the above problems, the technical solutions adopted by the present invention are as follows:
一种车船用碳基定型机油净化材料制备新方法，将具有特殊微结构的碳质吸附材料与高分子胶黏剂以一定比例均匀混合、固化成型制备具有独特网状结构的车船用碳基定型机油净化材料。该独特网状结构为织网-通道-孔道的体型结构，具备织网-通道的过滤作用以及孔道结构的吸附作用，净化性能好、容污量高且适用于车船大流量机油过滤需求。A new method for preparing carbon-based molding oil purification materials for vehicles and ships. Carbon adsorbent materials with special microstructures and polymer adhesives are uniformly mixed in a certain ratio and solidified to form carbon-based molding materials with a unique network structure for vehicles and ships. Oil purification materials. This unique mesh structure is a mesh-channel-pore structure, which has the filtration effect of the mesh-channel and the adsorption effect of the pore structure. It has good purification performance, high dirt holding capacity, and is suitable for large-flow oil filtration needs of vehicles and ships.
所述车船用碳基定型机油净化材料制备新方法，碳质吸附材料是经调控以微、中孔为主的颗粒活性炭，其孔结构分布比例为微孔率≤30％、中孔率30％～70％；优选微孔率21％～30％、中孔率44％～66％。The new method for preparing carbon-based stereotyped engine oil purification materials for vehicles and ships. The carbonaceous adsorption material is granular activated carbon that has been controlled to be mainly micro- and mesopores. Its pore structure distribution ratio is microporosity ≤ 30% and mesopores 30%. ~70%; preferably the microporosity is 21% to 30% and the mesoporosity is 44% to 66%.
所述车船用碳基定型机油净化材料制备新方法，碳质吸附材料是经调控其表面含有丰富氮、氧官能团的活性炭材料，其中含氮官能团含量为2％～15％、含氧官能团含量为1～6mmol/g，pH值为8～14；优选，含氮官能团含量为5.27％-13.43％、含氧官能团含量为2.05～3.85mmol/g，pH值为8.3～12.5。The new method for preparing carbon-based stereotyped engine oil purification materials for vehicles and ships. The carbonaceous adsorption material is an activated carbon material whose surface is controlled to contain rich nitrogen and oxygen functional groups. The content of nitrogen-containing functional groups is 2% to 15%, and the content of oxygen-containing functional groups is 1 to 6 mmol/g, pH value is 8 to 14; preferably, the content of nitrogen-containing functional groups is 5.27%-13.43%, the content of oxygen-containing functional groups is 2.05-3.85 mmol/g, and the pH value is 8.3-12.5.
所述车船用碳基定型机油净化材料制备新方法，高分子胶黏剂为树脂胶主体中添加反应助剂制备得到，具备耐油、耐高温且能通过可控胶结形成开孔型渗透胶膜，其中树脂胶主体为聚酯型聚氨酯、聚醚型聚氨酯、酚醛树脂、脲醛树脂、环氧树脂、甲苯二异氰酸酯或二苯基甲烷二异氰酸酯中的两种或多种复配制得，反应助剂为二乙胺、三乙醇胺、二乙烯二胺、乙酰胺或聚丙烯酰胺中的一种或多种的混合物。According to the new method for preparing carbon-based shaping engine oil purification materials for vehicles and ships, the polymer adhesive is prepared by adding reaction aids to the main body of the resin glue. It is oil-resistant and high-temperature resistant and can form an open-pore permeable adhesive film through controllable cementation. The main body of the resin glue is a mixture of two or more of polyester polyurethane, polyether polyurethane, phenolic resin, urea-formaldehyde resin, epoxy resin, toluene diisocyanate or diphenylmethane diisocyanate, and the reaction aid is One or a mixture of one or more of diethylamine, triethanolamine, diethylenediamine, acetamide or polyacrylamide.
所述车船用碳基定型机油净化材料制备新方法，成型工艺为：常温下可控胶结与加压成型，低温下固化，高温下熟化。具体步骤为：在常温下，碳质吸附材料与高分子胶黏剂按质量比为1∶1～10∶1均匀混合、可控胶结，后装填于模具中加压成型，成型压力为0.1～2.0kg/cm2、时间为10～30min；之后置于控温容器中低温下固化，固化温度为40～100℃、时间为20～90min；之后进一步在高温下熟化，熟化温度为100～300℃、时间为30～200min。优选，固化温度40～85℃、时间30～90min；熟化温度120～280℃、时间50～180min。 The new method for preparing carbon-based shaped engine oil purification materials for vehicles and ships, the molding process is: controllable cementation and pressure molding at normal temperature, solidification at low temperature, and maturation at high temperature. The specific steps are: at normal temperature, the carbonaceous adsorption material and the polymer adhesive are uniformly mixed and controllably cemented in a mass ratio of 1:1 to 10:1, and then loaded into the mold and pressurized for molding. The molding pressure is 0.1 to 10:1. 2.0kg/cm 2 , time is 10-30min; then placed in a temperature-controlled container for curing at low temperature, curing temperature is 40-100℃, time is 20-90min; and then further cured at high temperature, curing temperature is 100-300 ℃, time is 30~200min. Preferably, the curing temperature is 40-85°C and the time is 30-90 minutes; the aging temperature is 120-280°C and the time is 50-180 minutes.
所述车船用碳基定型机油净化材料制备新方法，包括以下步骤：The new method for preparing carbon-based shaping engine oil purification materials for vehicles and ships includes the following steps:
(1)通过二次活化、氧化改性、表面掺杂协同调控碳质吸附材料的微孔、中孔比例及其表面含氧官能团含量、含氮官能团含量和pH值；(1) Synergistically control the micropore and mesopore proportions of carbonaceous adsorption materials as well as the content of oxygen-containing functional groups, nitrogen-containing functional groups and pH value on the surface through secondary activation, oxidative modification, and surface doping;
(2)树脂胶主体中加入反应助剂，制得高分子胶黏剂；树脂胶主体与反应助剂的质量比为5∶1-30∶1；(2) Add a reaction aid to the main body of the resin glue to prepare a polymer adhesive; the mass ratio of the main body of the resin glue to the reaction aid is 5:1-30:1;
(3)向步骤(1)中调控后的碳质吸附材料中加入步骤(2)制得的高分子胶黏剂，室温下均匀混合、可控胶结并装填于固定模具中，加压成型后将模具置于控温容器中低温固化，固化结束后取出冷却至室温脱模，之后进一步在高温下熟化制得碳基定型机油净化材料。(3) Add the polymer adhesive prepared in step (2) to the carbonaceous adsorption material adjusted in step (1), mix it evenly at room temperature, controllably cement it and fill it in a fixed mold, and then press and mold it. The mold is placed in a temperature-controlled container for low-temperature solidification. After solidification, it is taken out and cooled to room temperature for demoulding. The mold is then further matured at high temperature to obtain a carbon-based shaping engine oil purification material.
上述方法制备得到的车船用碳基定型机油净化材料。The carbon-based shaped engine oil purification material for vehicles and ships is prepared by the above method.
有益效果：与现有的技术相比，本发明的优点包括：Beneficial effects: Compared with existing technology, the advantages of the present invention include:
1、本发明基于机油自身特性及使用过程中产生杂质的理化性质不同，如重金属、有机酸、胶质、灰尘等，通过调控碳质吸附材料的孔结构分布和构成，提高对不同分子、微粒大小的杂质的物理吸附作用，实现层级式吸附；同时，调控其表面含氧、含氮官能团含量和pH值，通过络合作用增强其对杂质的化学吸附作用。碳基吸附材料微结构和表面特性的调控与修饰，使其更适应于机油中杂质的去除，提高杂质吸附量和容污量，提升净化效果。1. Based on the characteristics of the engine oil itself and the different physical and chemical properties of impurities produced during use, such as heavy metals, organic acids, colloids, dust, etc., the present invention improves the sensitivity of different molecules and particles by regulating the pore structure distribution and composition of the carbonaceous adsorption materials. The physical adsorption of large and small impurities achieves hierarchical adsorption; at the same time, the content of oxygen-containing and nitrogen-containing functional groups and pH value on its surface are controlled to enhance its chemical adsorption of impurities through complexation. The regulation and modification of the microstructure and surface properties of carbon-based adsorption materials make them more suitable for the removal of impurities in engine oil, increase the adsorption capacity of impurities and dirt holding capacity, and improve the purification effect.
2、本发明通过高分子树脂胶的分子链反应形成的体型结构高分子胶黏剂，在高温机油中不溶解、不熔融、不润胀，具有良好的耐油、耐高温性和胶结强度，形成开孔型渗透胶膜，在保证良好的胶结强度的同时不堵塞碳质吸附材料原有孔结构，进而保持优良的吸附性能。2. The body-structured polymer adhesive formed by the molecular chain reaction of polymer resin glue in the present invention does not dissolve, melt or swell in high-temperature engine oil, and has good oil resistance, high temperature resistance and cementing strength, forming The open-pore permeable adhesive film ensures good bonding strength while not blocking the original pore structure of the carbonaceous adsorption material, thereby maintaining excellent adsorption performance.
3、本发明的车船用碳基定型机油净化材料具有独特网状结构，具备织网-通道结构的过滤作用以及活性炭孔道的吸附作用，容污量高、净化性能好且适用于车船大流量机油过滤需求，同时具备耐油、耐高温、成型可控、适应性广等优点，易于自动化、规模化生产。3. The carbon-based shaped engine oil purification material for vehicles and ships of the present invention has a unique mesh structure, has the filtering effect of the mesh-channel structure and the adsorption effect of the activated carbon pores, has high dirt holding capacity, good purification performance, and is suitable for large-flow engine oil in vehicles and ships. Filtration requirements, it also has the advantages of oil resistance, high temperature resistance, controllable molding, wide adaptability, etc., and is easy to automate and large-scale production.
附图说明Description of drawings
图1为碳基定型机油净化材料及其具备的织网-通道-孔道结构图。Figure 1 is a diagram of the carbon-based shaped oil purification material and its mesh-channel-pore structure.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例对本发明的具体实施方式做详细的说明。本发明公开的含氧官能团主要为酚羟基、羧基和羰基，含氮官能团主要为吡咯、吡啶和氮氧型，含氧官能团和含氮官能团的含量分别通过Bothem滴定法和XPS测定。In order to make the above objects, features and advantages of the present invention more obvious and understandable, specific implementation modes of the present invention will be described in detail below with reference to specific embodiments. The oxygen-containing functional groups disclosed in the present invention are mainly phenolic hydroxyl groups, carboxyl groups and carbonyl groups, and the nitrogen-containing functional groups are mainly pyrrole, pyridine and nitrogen-oxygen types. The contents of oxygen-containing functional groups and nitrogen-containing functional groups are measured by Bothem titration and XPS respectively.
实施例1Example 1
车船用碳基定型机油净化材料制备新方法，包括以下步骤：A new method for preparing carbon-based styling engine oil purification materials for vehicles and ships, including the following steps:
(1)通过二次活化、氧化改性、表面掺杂协同调控活性炭材料微孔率29.37％、中孔率 44.67％，表面含氧官能团含量为2.07mmol/g、含氮官能团含量为13.43％、pH值12.5；(1) Through secondary activation, oxidation modification, and surface doping, the microporosity and mesoporosity of activated carbon materials are controlled to 29.37% and 29.37%, respectively. 44.67%, the surface oxygen-containing functional group content is 2.07mmol/g, the nitrogen-containing functional group content is 13.43%, and the pH value is 12.5;
(2)树脂胶主体为聚醚型聚氨酯、酚醛树脂及甲苯二异氰酸酯按照质量比为2∶2∶1复配得到，之后按照质量比为10∶1添加反应助剂三乙醇胺，制成高分子胶黏剂；(2) The main body of the resin glue is polyether polyurethane, phenolic resin and toluene diisocyanate in a mass ratio of 2:2:1, and then the reaction aid triethanolamine is added in a mass ratio of 10:1 to make a polymer adhesive;
(3)常温下，向100g调控后的活性炭材料中加入50g高分子胶黏剂，快速搅拌、均匀混合、可控胶结，之后混合料装填于固定模具中，在成型压力为0.7kg/cm2下成型20min，之后将模具整体置于控温容器中在40℃下固化45min，后取出冷却至室温脱模，之后进一步在150℃下熟化90min，制得碳基定型机油净化材料。(3) At normal temperature, add 50g of polymer adhesive to 100g of regulated activated carbon material, stir quickly, mix evenly, and control cementation. Then the mixture is filled into a fixed mold, and the molding pressure is 0.7kg/cm 2 The mold was molded for 20 minutes, and then the entire mold was placed in a temperature-controlled container and cured at 40°C for 45 minutes, then taken out and cooled to room temperature for demoulding, and then further matured at 150°C for 90 minutes to obtain a carbon-based shaping engine oil purification material.
实施例2Example 2
车船用碳基定型机油净化材料制备新方法，包括以下步骤：A new method for preparing carbon-based styling engine oil purification materials for vehicles and ships, including the following steps:
(1)通过二次活化、氧化改性、表面掺杂协同调控活性炭材料微孔率25.21％、中孔率58.38％，表面含氧官能团含量为2.05mmol/g、含氮官能团含量为5.27％、pH值8.3；(1) Through secondary activation, oxidative modification, and surface doping, the activated carbon material has a microporosity of 25.21%, a mesoporosity of 58.38%, a surface oxygen-containing functional group content of 2.05mmol/g, and a nitrogen-containing functional group content of 5.27%. pH value 8.3;
(2)树脂胶主体为酚醛树脂、脲醛树脂按照质量比为1∶1进行复配，之后按照质量比8∶1添加反应助剂聚丙烯酰胺，制成高分子胶黏剂；(2) The main body of the resin glue is compounded with phenolic resin and urea-formaldehyde resin at a mass ratio of 1:1, and then the reaction aid polyacrylamide is added at a mass ratio of 8:1 to make a polymer adhesive;
(3)常温下，向100g调控后的活性炭材料中加入75g高分子胶黏剂，快速搅拌、均匀混合、可控胶结，之后混合料装填于固定模具中，在成型压力为1.4kg/cm2下成型30min，之后将模具整体置于控温容器中在75℃下固化30min，后取出冷却至室温脱模，之后进一步在280℃下熟化50min，制得碳基定型机油净化材料。(3) At normal temperature, add 75g of polymer adhesive to 100g of regulated activated carbon material, stir quickly, mix evenly, and control the cementation. Then the mixture is filled into a fixed mold, and the molding pressure is 1.4kg/cm 2 Molding for 30 minutes, then the entire mold was placed in a temperature-controlled container and cured at 75°C for 30 minutes, then taken out and cooled to room temperature for demoulding, and then further matured at 280°C for 50 minutes to obtain a carbon-based shaping engine oil purification material.
实施例3Example 3
车船用碳基定型机油净化材料制备新方法，包括以下步骤：A new method for preparing carbon-based styling engine oil purification materials for vehicles and ships, including the following steps:
(1)通过二次活化、氧化改性、表面掺杂协同调控活性炭材料微孔率21.17％、中孔率65.73％，表面含氧官能团3.03mmol/g、含氮官能团12.64％、pH值11.3；(1) Through secondary activation, oxidative modification, and surface doping, the microporosity of the activated carbon material is 21.17%, the mesoporosity is 65.73%, the surface oxygen-containing functional groups are 3.03 mmol/g, the nitrogen-containing functional groups are 12.64%, and the pH value is 11.3;
(2)树脂胶主体为酚醛树脂、脲醛树脂按照质量比1.5∶1进行复配，之后按照质量比10∶1添加反应助剂聚丙烯酰胺，制成高分子胶黏剂；(2) The main body of the resin glue is compounded with phenolic resin and urea-formaldehyde resin at a mass ratio of 1.5:1, and then the reaction aid polyacrylamide is added at a mass ratio of 10:1 to make a polymer adhesive;
(3)常温下，向100g调控后的活性炭材料中加入30g高分子胶黏剂，快速搅拌、均匀混合、可控胶结，之后混合料装填于固定模具中，在成型压力为1.0kg/cm2下成型30min，之后将模具整体置于控温容器中在60℃下固化45min，后取出冷却至室温脱模，之后进一步在200℃下熟化75min，制得碳基定型机油净化材料。(3) At normal temperature, add 30g of polymer adhesive to 100g of regulated activated carbon material, stir quickly, mix evenly, and control the cementation. Then the mixture is filled into a fixed mold, and the molding pressure is 1.0kg/cm 2 Molding for 30 minutes, then the entire mold was placed in a temperature-controlled container and cured at 60°C for 45 minutes, then taken out and cooled to room temperature for demoulding, and then further matured at 200°C for 75 minutes to obtain a carbon-based shaping engine oil purification material.
实施例4Example 4
车船用碳基定型机油净化材料制备新方法，包括以下步骤：A new method for preparing carbon-based styling engine oil purification materials for vehicles and ships, including the following steps:
(1)通过二次活化、氧化改性、表面掺杂协同调控活性炭材料微孔率21.17％、中孔率65.73％，表面含氧官能团3.03mmol/g、含氮官能团12.64％、pH值11.3； (1) Through secondary activation, oxidative modification, and surface doping, the microporosity of the activated carbon material is 21.17%, the mesoporosity is 65.73%, the surface oxygen-containing functional groups are 3.03 mmol/g, the nitrogen-containing functional groups are 12.64%, and the pH value is 11.3;
(2)树脂胶主体为聚酯型聚氨酯、环氧树脂、脲醛树脂及甲苯二异氰酸酯按照质量比为1∶1∶1∶1进行复配，之后按照质量比15∶1添加反应助剂二乙胺，制成高分子胶黏剂；(2) The main body of the resin glue is polyester polyurethane, epoxy resin, urea-formaldehyde resin and toluene diisocyanate, which are compounded in a mass ratio of 1:1:1:1, and then the reaction aid diethyl is added in a mass ratio of 15:1. Amine, made into polymer adhesive;
(3)常温下，100g调控后的活性炭材料中加入15g高分子胶黏剂，快速搅拌、均匀混合、可控胶结，之后混合料装填于固定模具中，在成型压力为1.0kg/cm2下成型30min，之后将模具整体置于控温容器中在65℃下固化90min，后取出冷却至室温脱模，之后进一步在150℃下熟化120min，制得碳基定型机油净化材料。(3) At normal temperature, add 15g of polymer adhesive to 100g of regulated activated carbon material, stir quickly, mix evenly, and control the cementation. Then the mixture is filled into a fixed mold, and the molding pressure is 1.0kg/cm 2 After molding for 30 minutes, the entire mold was placed in a temperature-controlled container and cured at 65°C for 90 minutes, then taken out and cooled to room temperature for demoulding, and then further matured at 150°C for 120 minutes to obtain a carbon-based shaping engine oil purification material.
实施例5Example 5
车船用炭基定型净化材料的制备方法，包括以下步骤：The preparation method of carbon-based styling and purification materials for vehicles and ships includes the following steps:
(1)通过二次活化、氧化改性、表面掺杂协同调控活性炭材料微孔率24.21％、中孔率58.36％，表面含氧官能团3.85mmol/g、含氮官能团10.57％、pH值9.7；(1) Through secondary activation, oxidative modification, and surface doping, the activated carbon material has a microporosity of 24.21%, a mesoporosity of 58.36%, a surface oxygen-containing functional group of 3.85 mmol/g, a nitrogen-containing functional group of 10.57%, and a pH value of 9.7;
(2)树脂胶主体为聚醚型聚氨酯、酚醛树脂及二苯基甲烷二异氰酸酯按照质量比为1∶1∶1进行复配，之后按照质量比25∶1添加反应助剂乙酰胺，制成高分子胶黏剂；(2) The main body of the resin glue is compounded with polyether polyurethane, phenolic resin and diphenylmethane diisocyanate in a mass ratio of 1:1:1, and then the reaction aid acetamide is added in a mass ratio of 25:1 to make polymer adhesive;
(3)常温下，向100g调控后的活性炭材料中加入20g高分子，快速搅拌、均匀混合、可控胶结，之后混合料装填于固定模具中，在成型压力为1.0kg/cm2下成型30min，之后将模具整体置于控温容器中在85℃下固化75min，后取出冷却至室温脱模，之后进一步在120℃下熟化180min，制得碳基定型机油净化材料。(3) At normal temperature, add 20g of polymer to 100g of regulated activated carbon material, stir quickly, mix evenly, and control cementation. Then the mixture is filled into a fixed mold and molded at a molding pressure of 1.0kg/ cm2 for 30 minutes. , then place the entire mold in a temperature-controlled container and solidify at 85°C for 75 minutes, then take it out and cool it to room temperature for demoulding, and then further mature it at 120°C for 180 minutes to prepare a carbon-based shaping oil purification material.
对比例1Comparative example 1
与实施例4不同的是所用活性炭为微孔率＞60％、表面含氧官能团含量为1.05mmol/g、无含氮官能团、pH 7.2。The difference from Example 4 is that the activated carbon used has a microporosity of >60%, a surface oxygen-containing functional group content of 1.05 mmol/g, no nitrogen-containing functional groups, and a pH of 7.2.
对比例2Comparative example 2
与实施例4不同的是所用高分子胶黏剂为单一树脂胶脲醛树脂、未进行复配。The difference from Example 4 is that the polymer adhesive used is a single resin, urea-formaldehyde resin, and is not compounded.
对比例3Comparative example 3
与实施例4不同的是所用高分子胶黏剂未添加反应助剂。The difference from Example 4 is that no reaction aid is added to the polymer adhesive used.
实施例1-5和对比例1-3的相关性能指标测试方法如下：采用含胶质(正戊烷不溶物)1.97％、铁含量83.47mg/Kg、铜含量43.15mg/Kg、铝含量36.21mg/Kg、酸值3.4mg/g的机油为原油，参照GB/T8028，在100℃下进行试验与指标测试，采用GB/T8926法测定机油中胶质(不溶物)，计算胶质去除率；采用GB/T17476电感耦合等离子发射光谱法测定机油中的铁、铜、铝含量，计算去除率和吸附容量；采用GB/T 7304测定机油酸值。测试结果如下表1所示：The relevant performance index testing methods of Examples 1-5 and Comparative Examples 1-3 are as follows: using colloid (n-pentane insoluble matter) 1.97%, iron content 83.47mg/Kg, copper content 43.15mg/Kg, aluminum content 36.21 mg/Kg, the engine oil with an acid value of 3.4mg/g is crude oil, refer to GB/T8028, carry out experiments and index tests at 100°C, use the GB/T8926 method to measure the colloid (insoluble matter) in the engine oil, and calculate the colloid removal rate ; Use GB/T17476 inductively coupled plasma emission spectrometry to determine the iron, copper, and aluminum content in engine oil, and calculate the removal rate and adsorption capacity; use GB/T 7304 to determine the acid value of engine oil. The test results are shown in Table 1 below:
表1实施例和对比例制备的碳基定型机油净化材料性能测试结果

Table 1 Performance test results of carbon-based styling oil purification materials prepared in Examples and Comparative Examples

表1中金属去除率、吸附量、胶质去除率以及酸值等数据可以看出，本发明的实施例1～5与对比例1～3相比，在高温机油净化中表现出更高的吸附容量、更大的容污量和更显著的净化效果，具备良好的耐油和耐高温性，更适应于高温机油的过滤净化。From the data of metal removal rate, adsorption capacity, colloid removal rate and acid value in Table 1, it can be seen that compared with Comparative Examples 1 to 3, Examples 1 to 5 of the present invention show higher performance in high-temperature oil purification. It has adsorption capacity, larger dirt holding capacity and more significant purification effect. It has good oil resistance and high temperature resistance, and is more suitable for filtration and purification of high temperature engine oil.
图1为碳基定型机油净化材料。其中，a为碳基定型机油净化材料具备的织网体型结构；b为碳基定型机油净化材料中活性炭颗粒间形成丰富的通道结构；c为碳基定型机油净化材料中活性炭表面形成的开孔型渗透胶膜，不堵塞活性炭材料原有的孔结构而保持其优良的吸附性能。 Figure 1 shows carbon-based styling oil purification materials. Among them, a is the mesh structure of the carbon-based shaped oil purification material; b is the rich channel structure formed between the activated carbon particles in the carbon-based shaped oil purification material; c is the openings formed on the surface of the activated carbon in the carbon-based shaped oil purification material type permeable membrane, which does not block the original pore structure of activated carbon materials and maintains its excellent adsorption performance.

Claims (4)

  1. 一种车船用碳基定型机油净化材料制备新方法，其特征在于，将具有特殊微结构的碳质吸附材料与高分子胶黏剂按质量比为1∶1～10∶1均匀混合、固化成型制备具有独特网状结构的车船用碳基定型机油净化材料；成型工艺为：常温下可控胶结与加压成型，40～100℃条件下固化，100～300℃条件下熟化；A new method for preparing carbon-based shaped engine oil purification materials for vehicles and ships, which is characterized by uniformly mixing carbonaceous adsorption materials with special microstructure and polymer adhesives in a mass ratio of 1:1 to 10:1, and solidifying them. Preparation of carbon-based shaping engine oil purification materials with a unique network structure for vehicles and ships; the molding process is: controllable cementation and pressure molding at normal temperature, solidification at 40-100°C, and maturation at 100-300°C;
    碳质吸附材料为以微、中孔为主的颗粒活性炭，其孔结构分布比例为微孔率≤30％、中孔率30％～70％；碳质吸附材料含有丰富氮、氧官能团，含氮官能团含量为2％～15％、含氧官能团含量为1～6mmol/g，pH值为8～14；The carbonaceous adsorption material is granular activated carbon with mainly micro and mesopores. Its pore structure distribution ratio is microporosity ≤ 30% and mesoporosity 30% to 70%. The carbonaceous adsorption material is rich in nitrogen and oxygen functional groups, and contains The content of nitrogen functional groups is 2% to 15%, the content of oxygen-containing functional groups is 1 to 6 mmol/g, and the pH value is 8 to 14;
    高分子胶黏剂为树脂胶主体中添加反应助剂制备得到，其中，树脂胶主体为聚酯型聚氨酯、聚醚型聚氨酯、酚醛树脂、脲醛树脂、环氧树脂、甲苯二异氰酸酯或二苯基甲烷二异氰酸酯中的两种或多种复配制得，反应助剂为二乙胺、三乙醇胺、二乙烯二胺、乙酰胺或聚丙烯酰胺中的一种或多种的混合物。The polymer adhesive is prepared by adding reaction aids to the main body of the resin glue. The main body of the resin glue is polyester polyurethane, polyether polyurethane, phenolic resin, urea-formaldehyde resin, epoxy resin, toluene diisocyanate or diphenyl. It is prepared by compounding two or more kinds of methane diisocyanate, and the reaction aid is one or more mixtures of diethylamine, triethanolamine, diethylenediamine, acetamide or polyacrylamide.
  2. 根据权利要求1所述车船用碳基定型机油净化材料制备新方法，其特征在于：成型工艺具体步骤为：在常温下，碳质吸附材料与高分子胶黏剂均匀混合、可控胶结，后装填于模具中加压成型，成型压力为0.1～2.0kg/cm2、时间为10～30min；之后置于控温容器中低温下固化，固化时间为20～90min；之后进一步在高温下熟化，熟化时间为30～200min。The new method for preparing carbon-based shaping engine oil purification materials for vehicles and ships according to claim 1, characterized in that: the specific steps of the molding process are: at normal temperature, the carbonaceous adsorption material and the polymer adhesive are uniformly mixed and controllably cemented, and then It is filled into the mold and pressed for molding. The molding pressure is 0.1~2.0kg/cm 2 and the time is 10~30min. It is then placed in a temperature-controlled container for solidification at low temperature and the curing time is 20~90min. It is then further cured at high temperature. The aging time is 30 to 200 minutes.
  3. 根据权利要求1所述车船用碳基定型机油净化材料制备新方法，其特征在于，包括以下步骤：The new method for preparing carbon-based shaping engine oil purification materials for vehicles and ships according to claim 1, characterized in that it includes the following steps:
    (1)通过二次活化、氧化改性、表面掺杂协同调控碳质吸附材料的微孔、中孔比例及其表面含氧官能团含量、含氮官能团含量和pH值；(1) Synergistically control the micropore and mesopore proportions of carbonaceous adsorption materials as well as the content of oxygen-containing functional groups, nitrogen-containing functional groups and pH value on the surface through secondary activation, oxidative modification, and surface doping;
    (2)树脂胶主体中加入反应助剂，制得高分子胶黏剂；树脂胶主体与反应助剂的质量比为5∶1-30∶1；(2) Add a reaction aid to the main body of the resin glue to prepare a polymer adhesive; the mass ratio of the main body of the resin glue to the reaction aid is 5:1-30:1;
    (3)向步骤(1)中调控后的碳质吸附材料中加入步骤(2)制得的高分子胶黏剂，室温下均匀混合、可控胶结并装填于固定模具中，加压成型后将模具置于控温容器中低温固化，固化结束后取出冷却至室温脱模，之后进一步在高温下熟化后制得碳基定型机油净化材料。(3) Add the polymer adhesive prepared in step (2) to the carbonaceous adsorption material adjusted in step (1), mix it evenly at room temperature, controllably cement it and fill it in a fixed mold, and then press and mold it. The mold is placed in a temperature-controlled container for low-temperature solidification. After solidification, it is taken out and cooled to room temperature for demoulding. The mold is then further matured at high temperature to obtain a carbon-based shaping engine oil purification material.
  4. 权利要求1-3任一所述方法制备得到的车船用碳基定型机油净化材料。 Carbon-based shaped engine oil purification material for vehicles and ships prepared by the method of any one of claims 1-3.
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Publication number Priority date Publication date Assignee Title
CN114699846B (en) * 2022-04-02 2023-03-17 中国林业科学研究院林产化学工业研究所 Novel preparation method of carbon-based setting engine oil purification material for vehicles and ships

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279696A1 (en) * 2001-08-23 2005-12-22 Bahm Jeannine R Water filter materials and water filters containing a mixture of microporous and mesoporous carbon particles
CN101143720A (en) * 2006-09-29 2008-03-19 北京化工大学 Active carbon micro-sphere absorption material and preparation method thereof
JP2009220098A (en) * 2008-02-18 2009-10-01 Nagoya Electrical Educational Foundation Adsorbent made of composite active carbon and its production method
CN101972630A (en) * 2010-11-12 2011-02-16 丽水市禾子净化设备有限公司 Manufacturing method of honeycomb type purification activated carbon
CN109160512A (en) * 2018-10-22 2019-01-08 中国林业科学研究院林产化学工业研究所 A kind of gasification of biomass residue pressed active carbon and preparation method thereof
CN112675616A (en) * 2020-12-24 2021-04-20 中国林业科学研究院林产化学工业研究所 Preparation method of activated carbon filter element for purifying engine oil
CN114699846A (en) * 2022-04-02 2022-07-05 中国林业科学研究院林产化学工业研究所 Novel preparation method of carbon-based forming engine oil purification material for vehicles and ships

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0506278D0 (en) * 2005-03-29 2005-05-04 British American Tobacco Co Porous carbon materials and smoking articles and smoke filters therefor incorporating such materials
CN111774031A (en) * 2020-08-06 2020-10-16 淄博鹏达环保科技有限公司 Carbon-based composite adsorbing material for adsorbing and removing industrial VOCs and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050279696A1 (en) * 2001-08-23 2005-12-22 Bahm Jeannine R Water filter materials and water filters containing a mixture of microporous and mesoporous carbon particles
CN101143720A (en) * 2006-09-29 2008-03-19 北京化工大学 Active carbon micro-sphere absorption material and preparation method thereof
JP2009220098A (en) * 2008-02-18 2009-10-01 Nagoya Electrical Educational Foundation Adsorbent made of composite active carbon and its production method
CN101972630A (en) * 2010-11-12 2011-02-16 丽水市禾子净化设备有限公司 Manufacturing method of honeycomb type purification activated carbon
CN109160512A (en) * 2018-10-22 2019-01-08 中国林业科学研究院林产化学工业研究所 A kind of gasification of biomass residue pressed active carbon and preparation method thereof
CN112675616A (en) * 2020-12-24 2021-04-20 中国林业科学研究院林产化学工业研究所 Preparation method of activated carbon filter element for purifying engine oil
CN114699846A (en) * 2022-04-02 2022-07-05 中国林业科学研究院林产化学工业研究所 Novel preparation method of carbon-based forming engine oil purification material for vehicles and ships

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Polymer Material", 30 June 2000, CHINA LIGHT INDUSTRY PRESS, CN, ISBN: 7-5019-2627-1, article LING, SHENG ET AL. EDITED: "5.2.3.2 Classification", pages: 153 - 157, XP009550123 *
CHEN XIAOHUI, XU RUTING, XU YANTING, HU HUI, PAN SHOUQUAN, PAN HONGKUN: "Natural adsorbent based on sawdust for removing impurities in waste lubricants", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 350, 1 May 2018 (2018-05-01), AMSTERDAM, NL , pages 38 - 45, XP093096225, ISSN: 0304-3894, DOI: 10.1016/j.jhazmat.2018.01.057 *

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