CN108329945A - A kind of preparation method of transformer oil anti-gassing component - Google Patents

A kind of preparation method of transformer oil anti-gassing component Download PDF

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Publication number
CN108329945A
CN108329945A CN201810173338.5A CN201810173338A CN108329945A CN 108329945 A CN108329945 A CN 108329945A CN 201810173338 A CN201810173338 A CN 201810173338A CN 108329945 A CN108329945 A CN 108329945A
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China
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tower
oil
solvent
preparation
hydrotreating
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CN201810173338.5A
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CN108329945B (en
Inventor
秦鸣
秦一鸣
马莉莉
齐邦峰
郭莎莎
张翠侦
李福起
徐岩峰
王伟
朱长申
焦祖凯
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China National Offshore Oil Corp CNOOC
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/14Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1037Hydrocarbon fractions

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of preparation methods of transformer oil anti-gassing component, include the following steps:S1, using catalytic cracked oil pulp as raw material, carried out hydrotreating and hydrofinishing, through distillation cut after obtain 400 DEG C of samples of <;S2, it 400 DEG C of samples of < is placed in solvent refining tower carries out solvent refining, collect Extract in the bottom of tower of the overhead collection raffinate of the solvent refining tower, the solvent refining tower, recycle solvent in the Extract, obtain tapped oil;S3, by the tapped oil by denitrifier Complex denitrogenation and clay-filtered, it is transformer oil anti-gassing component to collect refined oil.The degassing property of transformer oil, and addition≤3wt% can significantly be improved by transformer oil anti-gassing component made from the preparation method, do not influence product oxidation stability.

Description

A kind of preparation method of transformer oil anti-gassing component
Technical field
The present invention relates to transformer oil preparation fields, more particularly, to a kind of preparation side of transformer oil anti-gassing component Method.
Background technology
Currently, China comes into the fast-developing period of bulk power grid and extra-high voltage grid, EHV transformer is with special Transformer oil demand increases.EHV transformer requires preferable degassing property with special transformer oil.Become with changing The substance of depressor gassing properties of insulating oil effect is anti-gassing property component.In the composition of transformer oil, linear paraffin anti-gassing property is poor, virtue The anti-gassing property of hydrocarbon is good, but crossing polyaromatic especially polycyclic aromatic hydrocarbon influences the oxidation stability of product.
Chinese patent CN1438299A discloses the production method and its application method of transformer oil anti-gassing additive. This method is 250-500 DEG C of petroleum distillate as raw material using boiling point, carries out hydrotreating, and the generation oil of hydrotreating, will through distillation Boiling range fraction between 280-360 DEG C is concocted to obtain superelevation as transformer oil anti-gassing component with common transformer oil Pressure transformer oil.The anti-gassing component additive that this method obtains, really lube cut produce rubber using high-pressure hydrogenation Byproduct caused by filling oil, it is low that there is yields, invests high problem.
Chinese patent CN102676215A discloses a kind of method improving transformer oil anti-gassing performance, this method chaff Aldehyde, which refines tapped oil and raw material, to be had blending or is directly again introduced into furfural device with tapped oil, obtain ultrahigh voltage transformer oil or Person's anti-gassing property blending component.This method uses furfural treatment technique, to commercial introduction, needs that furfural device, investment is transformed Cost is big, is not easy industrialization promotion.
Chinese patent CN101747934B discloses a kind of preparation method of anti-evolving-gas additive of transformer oil, and this method is adopted It is raw material with 285-360 DEG C of fraction of naphthenic base viscous crude, anti-evolving-gas additive component is obtained by hydrofining technology.This method It needs to use hydrogenation technique, cost of investment is big, and the degassing property additive addition prepared is 5% or more, and addition is larger.
Invention content
The application technical problems to be solved are to provide the preparation method of transformer oil anti-gassing component;Pass through the preparation Transformer oil anti-gassing component made from method can significantly improve the degassing property of transformer oil, and addition≤3wt%, no Influence product oxidation stability.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
A kind of preparation method of transformer oil anti-gassing component, includes the following steps:
S1, using catalytic cracked oil pulp as raw material, carried out hydrotreating and hydrofinishing, through distillation cut after obtain < 400 DEG C of samples;
S2, it 400 DEG C of samples of < is placed in solvent refining tower carries out solvent refining, received in the tower top of the solvent refining tower Collect raffinate, the bottom of tower of the solvent refining tower collects Extract, recycles solvent in the Extract, obtain tapped oil;
S3, by the tapped oil by denitrifier Complex denitrogenation and clay-filtered, it is that transformer oil is anti-to collect refined oil Degassing property component.
As being further improved for technical solution, in step S1, the hydrotreating catalyst and hydrofining are urged Agent is one or more in following catalyst:Molybdenum-nickel type hydrogenation catalyst, tungsten-ni-type hydrogenation catalyst, molybdenum-cobalt type Hydrogenation catalyst, molybdenum-tungsten-ni-type hydrogenation catalyst.
As being further improved for technical solution, in step S1, the hydrotreating reaction temperature is 330-380 DEG C;It is excellent Select 350 DEG C -370 DEG C;The hydrofining reaction temperature is 230-290 DEG C;It is preferred that 260 DEG C -280 DEG C;Hydrogen and described plus hydrogen The volume parts ratio of oil is 600-1200:1;It is preferred that 800-1000:1;Hydrotreating volume space velocity is 0.2-1.0h-1;It is preferred that 0.4h-1-0.8h-1;Hydrofinishing volume space velocity is 0.2-1.0h-1;It is preferred that 0.4h-1-0.8h-1;The hydrotreating and plus hydrogen Refined pressure is 10-18MPa.
As being further improved for technical solution, in step S2, the solvent is furfural;The solvent and the distillate Mass ratio be 0.5~2.5:1;The temperature of the tower top of the solvent refining tower is 80~120 DEG C;The tower of the solvent refining tower The temperature at bottom is 45~75 DEG C;And the temperature of the bottom of tower of the solvent refining tower is lower than the temperature of the tower top of the solvent refining tower 20~30 DEG C.
As being further improved for technical solution, in step S3, the clay-filtered reaction temperature is 80 DEG C -140 DEG C; It is preferred that 80 DEG C -100 DEG C;Reaction time is 20min-50min;It is preferred that 30min-40min;Carclazyte addition is 1%-8%;It is preferred that 3%-5%.
Any range recorded in the present invention includes any numerical value between end value and end value and end value or end value Between the arbitrary subrange that is constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention The conventional equipment in fields can be used or carried out with reference to the prior art of fields.
Compared with prior art, the present invention has the advantages that:
Transformer oil anti-gassing component made from preparation method of the present invention can significantly improve the degassing property of transformer oil, And addition≤3wt%, product oxidation stability is not influenced.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this The protection domain of invention.
A kind of preparation method of transformer oil anti-gassing component, includes the following steps:
S1, using catalytic cracked oil pulp as raw material, carried out hydrotreating and hydrofinishing, through distillation cut after obtain < 400 DEG C of samples;
S2, it 400 DEG C of samples of < is placed in solvent refining tower carries out solvent refining, received in the tower top of the solvent refining tower Collect raffinate, the bottom of tower of the solvent refining tower collects Extract, recycles solvent in the Extract, obtain tapped oil;
S3, by the tapped oil by denitrifier Complex denitrogenation and clay-filtered, it is that transformer oil is anti-to collect refined oil Degassing property component.
Term " catalytic cracked oil pulp " in the present invention is for example given birth to from CNOOC Huizhou refinery company catalytic cracking unit Production.
According to the certain embodiments of the application, in step S1, the hydrotreating catalyst and hydrofining are urged Agent is one or more in following catalyst:Molybdenum-nickel type hydrogenation catalyst, tungsten-ni-type hydrogenation catalyst, molybdenum-cobalt type Hydrogenation catalyst, molybdenum-tungsten-ni-type hydrogenation catalyst.
According to the certain embodiments of the application, in step S1, the hydrotreating reaction temperature is 330-380 DEG C;It is excellent Select 350 DEG C -370 DEG C;Concretely 350 DEG C, 360 DEG C, 370 DEG C etc.;The hydrofining reaction temperature is 230-290 DEG C;It is excellent Select 260 DEG C -280 DEG C;Concretely 260 DEG C, 270 DEG C, 280 DEG C etc.;The volume parts ratio of hydrogen and the hydrogenated oil is 600- 1200:1;It is preferred that 800-1000:1;Concretely 800:1、900:1、1000:1 etc.;Hydrotreating volume space velocity is 0.2- 1.0h-1;It is preferred that 0.4h-1-0.8h-1;Concretely 0.4h-1、0.6h-1、0.8h-1Deng;Hydrofinishing volume space velocity is 0.2- 1.0h-1;It is preferred that 0.4h-1-0.8h-1;Concretely 0.4h-1、0.6h-1、0.8h-1Deng;The hydrotreating and hydrofinishing Pressure is 10-18MPa, can be 14MPa, 15MPa or 16MPa.It can guarantee product oxidation stability within the scope of above-mentioned parameter; It can guarantee that most of aromatic hydrocarbons is converted into monocycle and double ring arene.
According to the certain embodiments of the application, in step S2, the solvent is furfural;The solvent and the distillate Mass ratio be 0.5~2.5:1, concretely 1.0:1、1.5:1 or 2.0:1;The temperature of the tower top of the solvent refining tower is 80~120 DEG C, concretely 90 DEG C, 100 DEG C or 110 DEG C;The temperature of the bottom of tower of the solvent refining tower is 45~75 DEG C, specifically It can be 60 DEG C, 65 DEG C or 70 DEG C;And the temperature of the bottom of tower of the solvent refining tower is than the temperature of the tower top of the solvent refining tower Low 20~30 DEG C.It can guarantee product oxidation stability within the scope of above-mentioned parameter.
According to the certain embodiments of the application, in step S3, the clay-filtered reaction temperature is 80 DEG C -140 DEG C; It is preferred that 80 DEG C -100 DEG C;Concretely 80 DEG C, 90 DEG C, 100 DEG C etc.;Reaction time is 20min-50min;It is preferred that 30min- 40min;Concretely 30min, 35min, 40min etc.;Carclazyte addition is 1%-8%;It is preferred that 3%-5%;Concretely 3%, 4% and 5%.It can guarantee product oxidation stability within the scope of above-mentioned parameter.
Embodiment 1
A kind of preparation method of transformer oil anti-gassing component, includes the following steps:
1) using catalytic cracked oil pulp as raw material, hydropyrolysis experiment (Shanghai Mai Ruier experimental facilities is carried out adding hydrogen pilot-plant Co., Ltd produces, and two reactor series connection, single reactor catalyst maximum loadings are 200mL, and new hydrogen once passes through), The filling processing catalyst (LH-23) in first reactor, second reactor is built-in to fill out hydrofining catalyst (FV-10), detailed operating parameter is shown in Table 2.After carrying out distillation cutting to hydrofining oil, < is obtained after distillation is cut 400 DEG C of samples;
2) 400 DEG C of samples of < are placed in solvent refining tower and carry out solvent refining, Extract is collected in bottom of tower, described in recycling Solvent in Extract, obtains tapped oil;
3) by the tapped oil by denitrifier (such as:WSQ-5 types) Complex denitrogenation and bleaching earth adsorption, collecting refined oil is For transformer oil anti-gassing component.
From the data in table 2, it can be seen that the transformer oil anti-gassing component two ring aromatic content 84% prepared, total arene content 91%, degassing property is -51mm3Therefore/min it is excellent to be prepared into transformer oil anti-gassing constitutive property.
Comparative example 1
Comparative example 1 and embodiment 1 use identical feedstock oil, but raw material is without hydrotreating-hydrofining technology, directly It connects as the clay-filtered raw material of furfural treatment-, detailed operating parameter is shown in Table 2.Full fraction carries out after clay-filtered to furfural treatment- Sample is obtained after distillation cutting.
From the data in table 2, it can be seen that the transformer oil anti-gassing component two ring aromatic content 75% prepared, total arene content 89%, degassing property is -30mm3/min。
Embodiment 2
Embodiment 2 is identical with 1 processing flow of embodiment, and feedstock oil, furfurol test device, adds hydrogenation test apparatus Hydrogen processing catalyst, hydrofining catalyst, denitrifier, bleaching earth adsorption agent are also identical, concrete operations parameter and embodiment 1 Different (referring to table 2).
From the data in table 2, it can be seen that the transformer oil anti-gassing component two ring aromatic content 87% prepared, total arene content 93%, degassing property is -56mm3/min.Therefore, it is excellent to be prepared into transformer oil anti-gassing constitutive property.
Comparative example 2
Comparative example 2 and embodiment 2 use identical feedstock oil, direct hydrogenation processing-hydrofinishing raw material, but raw material without Furfural treatment-bleaching earth adsorption technique is crossed, detailed operating parameter is shown in Table 2.Distillation is carried out to the full fraction of hydrotreating-hydrofinishing to cut Sample is obtained after cutting.
From the data in table 2, it can be seen that the transformer oil anti-gassing component two ring aromatic content 57% prepared, total arene content 85%, degassing property is -20mm3/min。
Embodiment 3
Embodiment 3 is identical with 1 processing flow of embodiment, and feedstock oil, furfurol test device, adds hydrogenation test apparatus Hydrogen processing catalyst, Hydrobon catalyst, denitrifier, bleaching earth adsorption agent are also identical, and concrete operations parameter is different from embodiment 1 (referring to table 2).
From the data in table 2, it can be seen that the transformer oil anti-gassing component two ring aromatic content 91% prepared, total arene content 95%, degassing property is<-60mm3/min.Therefore, it is excellent to be prepared into transformer oil anti-gassing constitutive property.
Comparative example 3
A kind of preparation method of transformer oil anti-gassing component, includes the following steps:
1) by catalytic cracked oil pulp by denitrifier (such as:WSQ-5 types) Complex denitrogenation and bleaching earth adsorption, it collects refined Oil;
2) using refined oil as raw material, hydropyrolysis experiment (the limited public affairs of Shanghai Mai Ruier experimental facilities are carried out adding hydrogen pilot-plant Department's production, two reactor series connection, single reactor catalyst maximum loadings are 200mL, and new hydrogen once passes through), first Filling processing catalyst (LH-23) in a reactor, second reactor is built-in to fill out hydrofining catalyst (FV-10), Detailed operating parameter is shown in Table 2.After carrying out distillation cutting to hydrofining oil, 400 DEG C of samples of < are obtained after distillation is cut;
3) 400 DEG C of samples of < are placed in solvent refining tower and carry out solvent refining, Extract is collected in bottom of tower, described in recycling Solvent in Extract obtains product oil;
1 feedstock property of table
2 embodiment of table and comparative example property
The anti-gassing property component prepared in commercially available transformer oil and addition embodiment 1 is shown in Table 3 to the influence of its representative property.
Influence after 3 commercially available transformer oil of table and addition to its property
By table 2 and 3 data it is found that the total arene content height of transformer oil anti-gassing component, bicyclic virtue prepared by the present invention Hydrocarbon content is high, and anti-gassing property component prepared by the present invention is added in commercially available transformer oil and accounts for the 2.0% of mass percentage, energy It is obviously improved its degassing property, and other properties especially oxidation stability is not impacted substantially.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is every to belong to this hair Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.

Claims (7)

1. a kind of preparation method of transformer oil anti-gassing component, which is characterized in that include the following steps:
S1, using catalytic cracked oil pulp as raw material, carried out hydrotreating and hydrofinishing, through distillation cut after obtain < 400 DEG C sample;
S2, it 400 DEG C of samples of < is placed in solvent refining tower carries out solvent refining, taken out in the overhead collection of the solvent refining tower Extract is collected in the bottom of tower of extraction raffinate, the solvent refining tower, recycles solvent in the Extract, obtains tapped oil;
S3, by the tapped oil by denitrifier Complex denitrogenation and clay-filtered, it is transformer oil anti-gassing to collect refined oil Property component.
2. preparation method according to claim 1, it is characterised in that:In step S1, the hydrotreating catalyst and plus hydrogen Post-refining catalyst is one or more in following catalyst:Molybdenum-nickel type hydrogenation catalyst, tungsten-ni-type hydrogenation catalyst Agent, molybdenum-cobalt type hydrogenation catalyst, molybdenum-tungsten-ni-type hydrogenation catalyst.
3. preparation method according to claim 1, it is characterised in that:In step S1, the hydrotreating reaction temperature is 330-380℃;The hydrofining reaction temperature is 230-290 DEG C;The volume parts ratio of hydrogen and the hydrogenated oil is 600- 1200:1;Hydrotreating volume space velocity is 0.2-1.0h-1;Hydrofinishing volume space velocity is 0.2-1.0h-1;The hydrotreating Pressure with hydrofinishing is 10-18MPa.
4. preparation method according to claim 3, it is characterised in that:The hydrotreating reaction temperature is 350 DEG C -370 DEG C; The hydrofining reaction temperature is 260 DEG C -280 DEG C;The volume parts ratio of hydrogen and the hydrogenated oil is 800-1000:1;Add It is 0.4h-1-0.8h that hydrogen, which handles volume space velocity,-1;Hydrofinishing volume space velocity is 0.4h-1-0.8h-1;The hydrotreating and plus The refined pressure of hydrogen is 10-18MPa.
5. preparation method according to claim 1, it is characterised in that:In step S2, the solvent is furfural;The solvent with The mass ratio of the distillate is 0.5~2.5:1;The temperature of the tower top of the solvent refining tower is 80~120 DEG C;The solvent The temperature of the bottom of tower for the treatment of column is 45~75 DEG C;And the temperature of the bottom of tower of the solvent refining tower is than the tower of the solvent refining tower The temperature on top is 20~30 DEG C low.
6. preparation method according to claim 1, it is characterised in that:In step S3, the clay-filtered reaction temperature is 80℃-140℃;Reaction time is 20min-50min;Carclazyte addition is 1%-8%.
7. preparation method according to claim 6, it is characterised in that:In step S3, the clay-filtered reaction temperature is 80℃-100℃;Reaction time is 30min-40min;Carclazyte addition is 3%-5%.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109794273A (en) * 2019-02-20 2019-05-24 中国海洋石油集团有限公司 The preparation method of hydrotreating catalyst, preparation method and transformer oil base oil
CN111961513A (en) * 2020-08-18 2020-11-20 江苏双江能源科技股份有限公司 U-shaped transformer oil composition
CN115386393A (en) * 2022-07-05 2022-11-25 中海油气(泰州)石化有限公司 Preparation system and method of transformer oil anti-gassing component

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458574A2 (en) * 1990-05-21 1991-11-27 Exxon Research And Engineering Company Process for producing transformer oil from a hydrocracked stock
CN102676215A (en) * 2011-03-08 2012-09-19 中国石油天然气股份有限公司 Method for improving gassing resistance of transformer oil and equipment for producing transformer oil
CN104910959A (en) * 2015-05-18 2015-09-16 中国海洋石油总公司 Transformer oil antigassing additive and preparation method thereof
CN105087059A (en) * 2015-09-01 2015-11-25 中国海洋石油总公司 Anti-gassing component of transformer oil and preparation method of component

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458574A2 (en) * 1990-05-21 1991-11-27 Exxon Research And Engineering Company Process for producing transformer oil from a hydrocracked stock
CN102676215A (en) * 2011-03-08 2012-09-19 中国石油天然气股份有限公司 Method for improving gassing resistance of transformer oil and equipment for producing transformer oil
CN104910959A (en) * 2015-05-18 2015-09-16 中国海洋石油总公司 Transformer oil antigassing additive and preparation method thereof
CN105087059A (en) * 2015-09-01 2015-11-25 中国海洋石油总公司 Anti-gassing component of transformer oil and preparation method of component

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109794273A (en) * 2019-02-20 2019-05-24 中国海洋石油集团有限公司 The preparation method of hydrotreating catalyst, preparation method and transformer oil base oil
CN109794273B (en) * 2019-02-20 2021-12-17 中国海洋石油集团有限公司 Hydrotreating catalyst, preparation method thereof and preparation method of transformer oil base oil
CN111961513A (en) * 2020-08-18 2020-11-20 江苏双江能源科技股份有限公司 U-shaped transformer oil composition
CN115386393A (en) * 2022-07-05 2022-11-25 中海油气(泰州)石化有限公司 Preparation system and method of transformer oil anti-gassing component
CN115386393B (en) * 2022-07-05 2023-10-10 中海油气(泰州)石化有限公司 Preparation system and method of anti-gassing component of transformer oil

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