WO2022089534A1 - 一种合成有机酯型基础油的制备方法及应用 - Google Patents
一种合成有机酯型基础油的制备方法及应用 Download PDFInfo
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- WO2022089534A1 WO2022089534A1 PCT/CN2021/127030 CN2021127030W WO2022089534A1 WO 2022089534 A1 WO2022089534 A1 WO 2022089534A1 CN 2021127030 W CN2021127030 W CN 2021127030W WO 2022089534 A1 WO2022089534 A1 WO 2022089534A1
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- acid
- base oil
- water
- organic ester
- synthetic organic
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- 239000002199 base oil Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 24
- 239000000194 fatty acid Substances 0.000 claims abstract description 24
- 229930195729 fatty acid Natural products 0.000 claims abstract description 24
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims abstract description 14
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920005862 polyol Polymers 0.000 claims abstract description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims abstract description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 150000002895 organic esters Chemical class 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Chemical class 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000005524 ceramic coating Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000010696 ester oil Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000009417 prefabrication Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 230000017525 heat dissipation Effects 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract 2
- 238000005303 weighing Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- -1 pentaerythritol ester Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000005643 Pelargonic acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/08—Cooling; Ventilating
- H01F27/10—Liquid cooling
- H01F27/12—Oil cooling
- H01F27/125—Cooling by synthetic insulating and incombustible liquid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a preparation method and application of synthetic organic ester type base oil.
- Transformer oil is an important part of the safe and stable operation of the transformer. Its main functions in oil-immersed transformers are: transformer insulation; medium heat transfer; protection of transformer internal materials from moisture and oxygen erosion.
- Transformer insulating oil is usually made of deeply refined lubricating oil as base oil and then added with antioxidants. It is mainly used as a dielectric for electrical equipment.
- the main properties of transformer insulating oil are low temperature performance, oxidation stability and dielectric loss.
- transformer insulating oil mainly has the following types:
- Mineral oil 1) Mineral resources are non-renewable; 2) Non-biodegradable; 3) The ignition point is only about 170 °C, which cannot meet the requirements of EN45545-2 R14 and other standards for rail vehicles;
- Silicone oil 1) It is not biodegradable; 2) It cannot be mixed with other types of oil products, and independent equipment is required to switch between oil products;
- Natural ester high flash point, fully biodegradable, but natural ester insulating oil has poor oxidation stability and high freezing point at low temperature.
- Synthetic ester It is prepared by using pentaerythritol and fatty acid synthetic polyester as base oil, which is completely biodegradable, has high flash point/fire point, good compatibility with other types of oils, and has the advantages of excellent oxidation stability and low freezing point.
- the synthetic process that the existing method makes the base oil is complicated, the acid value and the dielectric loss are high, and the high impurity content cannot meet the requirements of the insulating oil, such as a kind of continuous decompression catalytic distillation of the patent number CN107501092A to prepare the pentaerythritol ester base oil
- the method is to use a vacuum catalytic rectification column, take pentaerythritol and fatty acid as raw materials, and solid acid as a catalyst to carry out esterification reaction at 230 ⁇ 280 ° C and -0.06 ⁇ -0.09MPa vacuum conditions, and the top of the vacuum catalytic distillation column. After the excess fatty acid and the generated water enter the flash tank to remove the water, the reflux ratio is adjusted, and the fatty acid is refluxed to continue the esterification reaction.
- the object of the present invention is to provide a preparation method of synthetic organic ester type base oil, the product prepared by the method of the present invention is used as the base oil of transformer insulating oil, which can not only meet the performance requirements of transformer insulating oil, but also has good biological Degradability, the preparation process has the characteristics of high production efficiency and low emission.
- a preparation method for synthesizing an organic ester type base oil the reactants and auxiliary reagents are weighed, and the reactants are mixed raw materials of polyol and fatty acid according to the molar ratio of hydroxyl and carboxyl groups of 1:4-5, and the auxiliary reagents It includes the following raw materials by weight: 5-15% of water-carrying agent, 10-20% of decolorizing agent, 0.1-2% of catalyst, and 0.1-2% of antioxidant.
- the polyol is selected from pentaerythritol, ⁇ carbon has no hydrogen atom, and there are many alcoholic hydroxyl groups, and the synthesized polyol ester has the characteristics of good oxidation stability and low pour point; the ingredients of the reactants in molar percentages are: 15-25% of pentaerythritol, 75-25% of fatty acid. 85%;
- fatty acid is made up of one or more in n-valeric acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, n-nonanoic acid, isooctanoic acid and isononanoic acid, further, when selecting multiple acids to mix, at least containing iso-nonanoic acid.
- the catalyst is one or more of organic acids, metal salts, and metal oxides mixed in proportion, wherein the metal oxide particles can be reused and do not account for the proportion of the formula: p-toluenesulfonic acid can be selected as the organic acid.
- metal salts can be selected from one or more of sodium citrate, sodium tripolyphosphate, dibutyltin maleate, etc.
- metal oxides can be selected from X- ⁇ type activated alumina, porous alumina ceramics, nano- ⁇ -nano oxide
- One or more of aluminum ceramic powder coating and four-needle nano-zinc oxide ceramic coating, composite porous active catalytic components are selected, the reaction temperature is low, the reaction rate is fast and the efficiency is high; preferably, the catalyst is metal oxidation
- the compound is mixed with at least one of organic acid and metal salt.
- the decolorizing agent is composed of a mixture of graphite powder, carbon powder, diatomite and white clay, and is based on the total weight of the decolorizing agent, wherein the weight ratio of the graphite powder and the carbon powder exceeds 50%.
- the described water-carrying agent is composed of one or more of benzene, toluene and p-xylene. Based on the total volume of the water-carrying agent, the ratio of p-xylene exceeds 60% by volume, and it is required to be stable in nature and can be water-soluble. Production of low-boiling azeotropes.
- the raw material also includes protective gas, and the protective gas adopts high-purity nitrogen.
- the preparation method of the synthetic organic ester type transformer insulating oil base oil of the present invention comprises the following steps:
- Catalyst preparation dissolve the water-soluble metal salt catalyst with a small amount of water in the container, add X- ⁇ type activated alumina with porous structure, porous alumina ceramics, nano- ⁇ -nano alumina ceramic powder coating, four The needle-shaped nano-zinc oxide ceramic coating is mixed with particles and a trace amount of wetting agent, stirred evenly, and left to stand under positive pressure conditions to make the metal salt catalyst settle and crystallize;
- the above-mentioned base oil is used to prepare insulating ester oil, which is applied to the insulation and heat dissipation of transformers, including the following preparation process: after the base oil is subjected to conventional decolorization, deacidification, dehydration and filtration processes, a small amount of oxidation stabilizer can be added to prepare insulating ester oil. .
- the synthetic organic ester insulating oil is light yellow, transparent and clear, density 0.9-1.0g/ml, viscosity (40°C, mm2/s): 30-35, viscosity (-20°C, mm2/s): 1400-1650,
- the ignition point is greater than 300°C
- the pour point is less than -48°C
- the flash point is greater than 250°C
- the physical and chemical properties meet the requirements of IEC61099.
- the beneficial effects of the invention are as follows: the above formula and process are used for base oil production, the source of raw materials is stable, the synthesis process is simple, the reaction rate is fast, and the production efficiency is high, the base oil meets the requirements of OECD 301F for complete biodegradability, and the performance after preparation meets IEC61099 Physical and chemical performance requirements for transformer insulating oil. After the above-mentioned base oil is used for process improvement and formula adjustment, it can be used for high-end oil products in the fields of lubrication and cooling.
- a preparation method for synthesizing organic ester type transformer insulating oil base oil adopts the following synthesis process:
- Step 1 catalyst preparation: dissolve the water-soluble metal salt catalyst with a small amount of water in the container, add X- ⁇ type activated alumina with porous structure, porous alumina ceramics, nano- ⁇ -nano alumina ceramic powder coating, The four-needle nano-zinc oxide ceramic coating is mixed with particles and a small amount of low-boiling point wetting agent, stirred evenly, and left to stand under positive pressure conditions to make the metal salt catalyst settle and crystallize.
- reaction system prefabrication embodiment 1-embodiment 3 carries out the synthesis of base oil respectively according to the formula in the following table 1, pentaerythritol and fatty acid are batched by molar percentage, and other components are batched by mass percentage, first take pentaerythritol, 60% The fatty acid, 50% decolorizing agent, water-carrying agent, and organic acid catalyst are placed in the reaction vessel, and the temperature is stirred and heated to 80-120 °C until the pentaerythritol is completely dissolved;
- Step 3 synthesis reaction: the temperature is raised to 160-180°C, the remaining fatty acid and solid catalytic particles are added, stirred for 2-5h, cooled and separated, and the supernatant is returned to the reaction system; keep the temperature constant, continue to distill for 0.5-3h until the water is completely distilled out; vacuum distillation for 1-3h, pressure below -0.1MPa (high-purity nitrogen protection can be selected);
- Step 4 the temperature is lowered to 120-150°C, the remaining 50% of the decolorizing agent and antioxidant are added, and the normal pressure is maintained for 10-60 minutes; the vacuum is quickly filtered to obtain the base oil and then put into a storage container.
- Step 5 preparation of ester oil: after conventional decolorization, deacidification, dehydration and filtration processes, a small amount of oxidation stabilizer can be added to prepare insulating ester oil.
- the above results show that the base oil prepared by the method of the present invention is excellent in various indexes after dehydration, deacidification and decolorization, and its performance meets the physical and chemical performance requirements of IEC61099 for transformer insulating oil.
- the synthesized polyol ester has the characteristics of good oxidation stability and low pour point; the composite porous active catalytic component is selected, the reaction temperature is low, the reaction rate is fast and the efficiency is high; the fatty acid used is a common normal/isomeric carboxylic acid , the source of raw materials is stable.
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种合成有机酯型基础油的制备方法及应用,称取反应物和辅助试剂进行酯化反应,所述的反应物为多元醇和脂肪酸按照羟基和羧基的摩尔比为1:4-5混合原料,所述的辅助试剂包括下述重量百分比的原料:带水剂5-15%,脱色剂10-20%,催化剂0.1-2%,抗氧剂0.1-2%;所述的多元醇选用季戊四醇;所述的脂肪酸由正戊酸、正己酸、正庚酸、正辛酸、正壬酸、异辛酸和异壬酸中的一种或多种组成。本发明方法制备的产品将其作为变压器绝缘油的基础油,不仅能够满足变压器绝缘油的性能要求,而且具有良好的生物降解性,制备工艺具有生产效率高、排放低等特点。
Description
本发明涉及一种合成有机酯型基础油的制备方法及应用。
目前中国多个城市都制定了城市轨道交通的建设发展规划,2020年底全国将有60多座城市开通运营线路超过8000km,轨道车辆以快速、安全、准点、节能、环保、舒适的优势成为人们日常出行的首选,高速轨道车辆不断升级革新,对牵引变压器用油也提出了新的要求。变压器油是变压器安全稳定运行的重要组成部分,在油浸式变压器中主要作用有:变压器绝缘;介质传热;保护变压器内部材质免受水分、氧的侵蚀。
变压器绝缘油通常由深度精制的润滑油作为基础油,然后再加入抗氧化剂调制而成,其主要用作电器设备的电介质,变压器绝缘油的主要性能是低温性能、氧化安定性和介质损失。目前变压器绝缘油主要有以下几种类型:
矿物质油:1)矿物资源不可再生;2)不能生物降解;3)燃点仅170℃左右,不能满足轨道车辆用EN45545-2 R14等标准要求;
有机硅油:1)不可生物降解;2)与其他类型的油品不能混合使用,油品之间切换需要使用独立设备;
天然酯:燃点高、可完全生物降解,但天然酯绝缘油氧化安定性差和低温凝点高。
合成酯:采用季戊四醇与脂肪酸合成多元酯作为基础油制备而成,可完全生物降解、闪点/燃点高、与其他类型油相容性好、并且具有优良的氧化安定性、凝点低等优势,但现有方法制成基础油的合成工艺复杂,酸值、介质损耗高,且杂质含量高不能满足绝缘油的要求,如专利号为CN107501092A的一种连续减压催化蒸馏制备季戊四醇酯基础油的方法,采用减压催化精馏塔,以季戊四醇、脂肪酸为原料,固体酸为催化剂,在230~280℃,-0.06~-0.09MPa真空条件下进行酯化反应,减压催化蒸馏塔塔顶多余的脂肪酸和生成的水进入闪蒸罐去除水后,调节回流比,脂肪酸进行回流继续酯化反应,塔釜粗产品经过滤后获得高品质季戊四醇酯润滑油。
本发明的目的在于提供一种合成有机酯型基础油的制备方法,通过本发明方法制备的产品将其作为变压器绝缘油的基础油,不仅能够满足变压器绝缘油的性能要求,而且具有良好的生物降解性,制备工艺具有生产效率高、排放低等特点。
一种合成有机酯型基础油的制备方法,称取反应物和辅助试剂,所述的反应物为多元醇和脂肪酸按照羟基和羧基的摩尔比为1:4-5混合原料,所述的辅助试剂包括下述重量百分比的原料:带水剂5-15%,脱色剂10-20%,催化剂0.1-2%,抗氧剂0.1-2%。
所述多元醇选用季戊四醇,β碳没有氢原子,醇羟基多,合成的多元醇酯具有氧化安定性好,倾点低等特点;反应物按摩尔百分比配料:季戊四醇15-25%,脂肪酸75-85%;
所述的脂肪酸由正戊酸、正己酸、正庚酸、正辛酸、正壬酸、异辛酸和异壬酸中的一种或多种组成,进一步的,选用多种酸混合时至少含有异壬酸与从正壬酸、异辛酸中选取的一种混合,其中正壬酸与异壬酸在脂肪酸体系中总的摩尔数占比不超过20%,异辛酸与异壬酸在脂肪酸体系中总的摩尔数占比不超过45%,采用的脂肪酸未常见正构、异构羧酸,原料来源稳定;
所述的催化剂为有机酸、金属盐、金属氧化物中的一种或多种按比例混合,其中金属氧化物颗粒可重复使用,不占配方比例:其中有机酸可选用对甲基苯磺酸,金属盐可选用柠檬酸钠、三聚磷酸钠、马来酸二丁基锡等一种或多种,金属氧化物可选用X-ρ型活性氧化铝、多空氧化铝陶瓷、纳米α-纳米氧化铝陶瓷粉涂层、四针状纳米氧化锌陶瓷涂层的一种或多种,选用复合多孔活性型催化组分,反应温度低、反应速率快效率高;优选的,所述催化剂为金属氧化物与有机酸、金属盐两者中至少一种混合。
所述的脱色剂为石墨粉、碳粉、硅藻土、白土混合组成,以脱色剂的总重量为基准,其中石墨粉和碳粉的重量比例超过50%。
所述的带水剂由苯、甲苯、对二甲苯中的一种或多种组成,以带水剂的总体积为基准,其中对二甲苯的比例超过60体积%,要求性质稳定并可水生产低沸点共沸物。
所述原料中还包括保护气体,保护气体采用高纯氮气。
本发明合成有机酯型变压器绝缘油基础油的制备方法,它包括如下步骤:
1)催化剂制备:容器中用少量水溶解可水溶性的金属盐催化剂,加入具有多孔结构的X-ρ型活性氧化铝、多空氧化铝陶瓷、纳米α-纳米氧化铝陶瓷粉涂层、四针状纳米氧化锌陶瓷涂层混配颗粒和微量润湿剂,搅拌均匀后在正压条件下静置,使金属盐催化剂沉降结晶;
2)反应体系预制:取称量好的上述原料中的季戊四醇、60%的脂肪酸、50%脱色剂、带水剂、有机酸催化剂于反应容器中,搅拌升温至80-120℃至季戊四醇完全溶解;
3)合成反应:温度升高至160-180℃,加入剩余脂肪酸、步骤1)得到的固体催化颗粒,搅拌2-5h,冷却分离上清液返回反应体系;保持温度恒定,持续蒸馏0.5-3h至水分完全馏出;然后减压蒸馏1-3h,压力-0.1MPa以下,可选择高纯氮气保护。
4)温度降低至120-150℃,加入剩余50%脱色剂、抗氧剂,常压保持10-60min;然后快速负压抽滤,得基础油后装入储存容器。
采用上述基础油配制绝缘性酯油,应用于变压器的绝缘与散热,包括以下调配过程:基础油采用常规脱色、脱酸、脱水及过滤工艺后,加入少量氧化稳定剂可制备成绝缘性酯油。
该合成有机酯绝缘油为淡黄色,透明清澈,密度0.9-1.0g/ml,粘度(40℃,mm2/s):30-35、粘度(-20℃,mm2/s):1400-1650,燃点大于300℃,倾点小于-48℃,闪点大于250℃,理化性能满足IEC61099要求。
本发明的有益效果在于:采用上述配方及工艺进行基础油生产,原料来源稳定,合成工艺简单,反应速率快,生产效率高,基础油达到OECD 301F可完全生物降解要求,经调配后性能满足IEC61099对变压器绝缘油的理化性能要求。采用上述基础油经过工艺改进和配方调整后,可用于润滑、冷却等领域的高端油类产品。
应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1-实施例3
一种合成有机酯型变压器绝缘油基础油的制备方法,采用如下合成工艺:
步骤1,催化剂制备:容器中用少量水溶解可水溶性的金属盐催化剂,加入具有多孔结构的X-ρ型活性氧化铝、多空氧化铝陶瓷、纳米α-纳米氧化铝陶瓷粉涂层、四针状纳米氧化锌陶瓷涂层混配颗粒和微量低沸点润湿剂,搅拌均匀后在正压条件下静置,使金属盐催化剂沉降结晶。
步骤2,反应体系预制:实施例1-实施例3分别按照下述表1中的配方进行基础油的合成,季戊四醇和脂肪酸按摩尔百分比配料,其他组分按质量百分比配料,先取季戊四醇、60%的脂肪酸、50%的脱色剂、带水剂、有机酸催化剂于反应容器中,搅拌升温至80-120℃至季戊四醇完全溶解;
步骤3,合成反应:温度升高至160-180℃,加入剩余脂肪酸、固体催化颗粒,搅拌2-5h,冷却分离上清液返回反应体系;保持温度恒定,持续蒸馏0.5-3h至水分完全馏出;减压蒸馏1-3h,压力-0.1MPa以下(可选择高纯氮气保护);
步骤4,温度降低至120-150℃,加入剩余50%脱色剂、抗氧剂,常压保持10-60min;减压快速抽滤,得基础油后装入储存容器。
步骤5,酯油调配:采用常规脱色、脱酸、脱水及过滤工艺后,加入少量氧化稳定剂可制备成绝缘性酯油。
表1
基础油除水脱酸脱色后进行下述性能测试,结果如下表2:
表2
上述结果表明,采用本发明方法制备的基础油除水脱酸脱色后各项指标优良,性能满足IEC61099对变压器绝缘油的理化性能要求,选用的季戊四醇为多元醇,β碳没有氢原子,醇羟基多,合成的多元醇酯具有氧化安定性好,倾点低等特点;选用复合多孔活性型催化组分,反应温度低、反应速率快效率高;采用的脂肪酸为常见正构/异构羧酸,原料来源稳定。
以上仅为本发明的优选实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
- 一种合成有机酯型基础油的制备方法,其特征在于,称取反应物和辅助试剂进行酯化反应,所述的反应物为多元醇和脂肪酸按照羟基和羧基的摩尔比为1:4-5混合原料,所述的辅助试剂包括下述重量百分比的原料:带水剂5-15%,脱色剂10-20%,催化剂0.1-2%,抗氧剂0.1-2%;所述的多元醇选用季戊四醇;所述的脂肪酸由正戊酸、正己酸、正庚酸、正辛酸、正壬酸、异辛酸和异壬酸中的一种或多种组成。
- 根据权利要求1所述的合成有机酯型基础油的制备方法,其特征在于,选用多种酸混合时至少含有异壬酸与从正壬酸、异辛酸中选取的一种混合,其中正壬酸与异壬酸在脂肪酸体系中总的摩尔数占比不超过20%,异辛酸与异壬酸在脂肪酸体系中总的摩尔数占比不超过45%。
- 根据权利要求2所述的合成有机酯型基础油的制备方法,其特征在于,所述的催化剂为有机酸、金属盐、金属氧化物中的一种或多种按比例混合,其中金属氧化物颗粒可重复使用,不占配方比例:其中有机酸可选用对甲基苯磺酸,金属盐可选用柠檬酸钠、三聚磷酸钠、马来酸二丁基锡等一种或多种,金属氧化物可选用X-ρ型活性氧化铝、多空氧化铝陶瓷、纳米α-纳米氧化铝陶瓷粉涂层、四针状纳米氧化锌陶瓷涂层的一种或多种。
- 根据权利要求3所述的合成有机酯型基础油的制备方法,其特征在于,所述催化剂为金属氧化物与有机酸、金属盐两者中至少一种混合。
- 根据权利要求4所述的合成有机酯型基础油的制备方法,其特征在于,所述的脱色剂为石墨粉、碳粉、硅藻土、白土混合组成,以金属粉的总重量为基准,其中石墨粉和碳粉的重量比例超过50%。
- 根据权利要求5所述的合成有机酯型基础油的制备方法,其特征在于,所述的带水剂由苯、甲苯、对二甲苯中的一种或多种组成,以带水剂的总体积为基准,其中对二甲苯的比例超过60%。
- 根据权利要求6所述的合成有机酯型基础油的制备方法,其特征在于,所述原料中还包括保护气体,保护气体采用高纯氮气。
- 根据权利要求7所述的合成有机酯型基础油的制备方法,其特征在于,包括如下步骤:1)催化剂制备:容器中用少量水溶解可水溶性的金属盐催化剂,加入具有多孔结构的X-ρ型活性氧化铝、多空氧化铝陶瓷、纳米α-纳米氧化铝陶瓷粉涂层、四针状纳米氧化锌陶瓷涂层混配颗粒和微量润湿剂,搅拌均匀后在正压条件下静置,使金属盐催化剂沉降结晶;2)反应体系预制:取称量好的上述原料中的季戊四醇、60%的脂肪酸、50%脱色剂、带水剂、有机酸催化剂于反应容器中,搅拌升温至80-120℃至季戊四醇完全溶解;3)合成反应:温度升高至160-180℃,加入剩余脂肪酸、步骤1)得到的固体催化颗粒,搅拌2-5h,冷却分离上清液返回反应体系;保持温度恒定,持续蒸馏0.5-3h至水分完全馏出;然后减压蒸馏1-3h,压力-0.1MPa以下,可选择高纯氮气保护;4)温度降低至120-150℃,加入剩余50%脱色剂、抗氧剂,常压保持10-60min;然后快速负压抽滤,得基础油后装入储存容器。
- 根据权利要求1-8任一所述合成有机酯型基础油的应用,其特征在于,应用于变压器的绝缘与散热,包括以下调配过程:基础油采用常规脱色、脱酸、脱水及过滤工艺后,加入少量氧化稳定剂可制备成绝缘性酯油。
- 根据权利要求9所述合成有机酯型基础油的应用,其特征在于,该合成有机酯绝缘油为淡黄色,透明清澈,密度0.9-1.0g/ml,粘度(40℃,mm2/s):30-35、粘度(-20℃,mm2/s):1400-1650,燃点大于300℃,倾点小于-48℃,闪点大于250℃。
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