DE1594421C3 - Mineral oil-based insulating oil and process for the production of a mineral oil-based insulating oil - Google Patents

Description

3 4

Preferably, the heavy cycle gas oil is used before after performing one or more of the above

added to its addition to the oil base by distillation in the treatments described to the oil base

Atmospheric pressure; topped off so far that they are under. The addition is preferably made after the

350 ⁰ C boiling components are driven off. Oil base treated with a selective solvent

In addition, the heavy cycle gas oil has been used before 5 in order to reduce its aromatic content,

its addition to the oil base, preferably dewaxed, and as a rule it takes place before the final treatment,

if the finished oil has a cloud point (ASTM e.g. before treatment with natural or active

D 97-47) should have less than + 5 ° C. To z. B. fourth earth or preferably before treatment

an oil with a cloud point of -15 ⁰ C to with hydrogen.

must be a heavy cycle gas oil with an io. The oil base can also be used with the untreated

Pour point of -15 ° C can be used, and this or one or more of the above-described

can be treated by known dewaxing processes in benen processes heavy cycle gas oil

a yield of, for example, 80 to 85% are mixed, after which the two constituents

be won. individually for themselves such a finished treatment

The dewaxing treatment changes in none of the 15 throws.

Way the other properties that the finished - The amount of treated or to be added

oil mixture through the addition of the heavy cycle untreated heavy cycle gas oil is pre-

gas oil are awarded, in particular not the preferably 1 to 5 percent by weight, based on the

Resistance to oxidation. oil based.

To the aromatic content of the heavy circulatory 20
to increase gas oil, it can, regardless of whether

it is dewaxed or not, before it is added to the ice cream 1 1
oil based by treating with a selective solvent, e.g. B. phenol, are refined so that

an extract yield of 80 to 95%> preferably 25

from 90 to 95%. The starting material is a fluidized bed

The heavy cycle gas oil obtained is preferably also split with heavy cycle gas oil, regardless of whether it has been dewaxed with a viscosity of 2 cSt at 98.9 ° C. This starting material or has been treated with a selective solvent after various pretreatments or not, before its addition to the oil base 30 a light raffinate to obtain various a mild acid treatment, ζ. B. insulating oils added to a treatment. The light raffinate is recovered at 5 to 20%. preferably 8 to 12% 98 percent strength by submitting, for example, a light Tia Juana sulfuric acid. The acid tars are distillate so refined with phenol that a then, z. B. by hot decanting (at 80 to 100 ⁰ C), raffinate separated with a viscosity weight constant of, and the acid raffinate is obtained, for example with 35 0.822 (raffinate yield 55%).
aqueous or alcoholic sodium or potassium hydroxide solution, the oils consisting of the raffinate alone and neutralized, then washed with water and dried the mixtures of the raffinate and the various, z. B. with the help of natural adsorption products specified above are ready for use. earth (silicoaluminate). position a mild hydrogenation among the following

The heavy cycle gas oil as such or subject to 40 conditions:

Temperature '. , 280 ⁰ C '...

"60at pressure

_. , . .... I parts of oil / hour \ "" ,, _. ■ _Λ , '

Throughput speed, -1, V / V / hr 1

\ Catalyst room part /

■ ■ "..,, -j. ,. 7 space part hydrogen at NTP / hour \ _1cn

Flow velocity, I 150

\ Room part oil / hour J

Cobalt molybdate catalyst

Aluminum oxide

(3.5% CoO + 12.5%

MoO ₃ )

To determine the resistance to oxidation of these divorces and the percentage loss of strength

The so-called B. B. C. test is used to determine the cotton thread. In addition, after

for 1000 ml of the oil in a copper pot, the dielectric loss in 168 hours, i.e. H. the The presence of a cotton thread heated to 110 ° C. 65 tangent of the loss angle of the oxidized oil

will. Determinations are made after 72 hours and after 168 hours.

The NPA Color (ASTM D-155) and Acid Number The results are from the following tables

(ASTM D-947) of the oil as well as the amount of Ab- can be seen. >

table

properties

Products

C ₂

Tag Robinson Color

BBC test
After 72 hours

ASTM color

Acid number (mg ROH / g)

Sludge, g:

% Loss of strength of the cotton thread After 168 hours

ASTM color

Acid number (mg KOH / g)

Mud, g

% Loss of strength of the cotton thread

Tangent of the loss angle

Product A:
Product B:

11th

0.224
0.095
0

8+ 0.560

0.275

18th

0.168
0.064
0

V ₂
0.402
0.095
10
0.4200

22.5

0.063
0.008
0

0.126

0.048

0.1450

24

0.042
sense
0

V ₂
0.084
0.023
20th
0.0418

23

0.084
0.012
0

V ₂
0.168
0.037
24
0.0450

Light Tia Juana raffinate + 4% dewaxed heavy cycle gas oil.

Corresponds to product A after treatment with 2% activated fuller's earth (Actisil) at 85 ° C. while passing through nitrogen and 2% natural fuller's earth (Clarsil PCS) at HO ⁰ C

V ₂ hours

V for ₂ hours with nitrogen bubbling through.

Product C: Corresponding to product A after treatment with hydrogen at a pressure of 60 bar flow rate VVH = 1 gas ratio 150..

C ₁
C ₂

C ₃

250 ⁰ C
280 °. C.
300 ⁰ C

Table II

properties

3 B. Products D. E. A. 0.098 A- C. 3V ₂ - 3V ₂ - 0.008 0.063 4- 0.063 0.063 0 0.013 0.084 0.020 0.014 4+ 0 0.021 0 0 0.224 5 0 4V ₂ - 4 ¹ ar 0.055 0.119 4V ₂ - 0.105 0.098 10 0.050 0.112 0.040 0.042 0.2750 0 0.068 22nd 12th 0.0605 19th 0.0620 0.0740 0.0635

BBC test
After 72 hours

ASTM color

Acid number (mg KOH / g) ...:

Mud, g; ...

% Loss of strength of the cotton thread

After 168 hours

ASTM color

Acid number (mg KOH / g) '

Mud, g

0.042 tracks ■ 0

% Loss of strength of the cotton thread Tangent of the loss angle

V ₂

0.084 0.023 20
0.0418

Product A: Hydrogenated light raffinate at 280 ° C, a pressure of 60 bar, flow rate VVH = 1,

Gas ratio 150.

Product B: A product in accordance with separately hydrogenated B) = 250 ⁰ C - sulfur% .1,76

Product C: dewaxed heavy cycle gas oil Q = 280

Product D: (hydrogenation at 60 bar, flow rate D) = 320

Product E: VVH = 1, gas ratio 150) ■. E) = 350

Product F: hydrofined mixture (light raffinate + 4% dewaxed heavy cycle gas oil) 28O ⁰ C, 60 bar, flow velocity VVH = 1, gas ratio 150th

C-% 1.48 sulfur C-% 0.79 sulfur C-% 0.40 sulfur

Example 2

The starting material is a heavy circulating gas oil obtained by fluidized bed splitting a viscosity of 3.88 cSt at 98.9 ° C. This heavy cycle gas oil (C) becomes the following Products manufactured:

(C 1) Dewaxed product

Manufactured by dewaxing the heavy cycle gas oil (C) by cooling a solution of Space part of heavy circulating gas oil (C) in 3 space parts sec. Bring butyl acetate to - 25 ° C and filter off with a yield of 85%.

(C 2) Acid treated dewaxed product

Prepared by treating Cl at 10 ° / ₀ 98% sulfuric acid, decanting the acid tars at 90 ⁰ C, neutralizing the Säureraffinates with aqueous sodium hydroxide, washing with water and drying by natural Adsorptionserde (yield 75%, based on C 1).

7 8

These different products have the following characteristics:

product C2 C. Cl 1.015 1,000 1.010 3.93 3.88 4.05 178 174 174 45.8 56.6 46.8 -11 +33 -15 1,580 1.5764 1.5881 265 260 .265 64.5 ■ 61.75 69.0 ν 2.55 2.23 2.48 0.005 0.095 0.117

Density at 15 ° C, g / cm ³

Viscosity at 98.9 ° C, cSt

Flash point (open vessel), ° C

Aniline point, ° C

Cloud Point (ASTM D 97-47), ° C

Refractive index at 70 ⁰ C

Average molecular weight

Aromatic carbon content (by Ultrarotbestimmung) ^_0/0

Sulfur, weight percent

Nitrogen, weight percent

Using the dewaxed product C 1 and the acid treated dewaxed one Product C 2 are from the described in Example 1- light raffinate produced as oil-based insulating oils. .

The oils consisting only of the light raffinate as well as the mixtures of the oil base with the relevant ones Products are under the conditions of the hydrogenation carried out in Example 1 of the finishing treatment subject.

The oxidation resistance of these insulating oils is determined according to the BBC test described in Example 1 and a so-called CEI test method, in which ^{oxygen is passed through 25 g of oil in a glass tube in the presence of a copper wire at 100 °} C. at a rate of 11 / hour. is passed through. After 164 hours, the amount of deposits and the acid number of the oxidized oil are determined. These studies provide the following results:

none additive
4%> C1 . 4% C2 BBC test
After 72 hours
NPA color 3
0.098
0.008
0
4+
0.224
0.055
10
0.2750
0.220
0.020 2
0.042
sense
0
0.084
0.023
20th
0.0418
0.056
0.010 2
0.042
sense
0 Acid number, mg KOH / gw
Deposits, g.
Loss of strength of the cotton thread, ° / o
After 168 hours
NPA dye 0.100
0.018
20th
0.0650
0.022
0.008 Acid number, mg KOH / g
Deposits, g
Loss of strength of the cotton thread, ° / ₀
Tangent of the loss angle
CEI test '
Acid number, mg KOH / g
Deposits, g

309 641/191

Claims (6)

were obtained, then refined by treatment with pattansoriiche · m ^ sulfuric acid, sodium hydroxide solution and an absorbent in order to obtain products with a high aromatic content. The usage 1. Insulating oil, consisting of .5 a heavy cycle gas oil with defined physi calical data which has been hydrogenated a) a mineral oil, preferably a raffinate ^au s of the relevant literature is not taken and a light distillate. It is also known to make insulating oils by blending them b) 0.1 to 10 weight percent, based on the _{10 e} Jnes ordinary mineral oil with a synthetic weight of the mineral oil to produce an oxidation-oil, which in turn is a a _za tion of polynuclear aromatic hydrocarbon-density of 15 ° between Kondenhindernden hydrogenation 0, 99 and 1.10 g / ccm, substances with a viscosity at 98.9 ° by the Fischer-Tropsch process of 2 to 8 cSt, generated hydrocarbon fraction with the help of an aniline point in the order of ₁₅ Friedel-Craft -Catalyst has been obtained. 25 to 80 ° and a distillation range at Finally, an insulating oil is also known that is made from Atmospheric pressure of 180 to 660 ° on a mineral oil mixture with the addition of a carbon point heavy cycle gas oil. Hydrogen mixture, which by cracking, ; catalytic hydrogenation or alkylation obtained 2. Method for producing an insulating oil 20 has been established. This additive is in accordance with the addition according to claim 1, characterized in that the. Invention not to be compared. The known the heavy cycle gas oil before or after the additive should boil between 160 and 350 ° C while Mixing with the mineral oil is hydrogenated. the boiling range of the additive according to the invention 3. Process for the production of an insulating oil between 350 and 660 ° C. according to claim 2, characterized in that there is the isody according to the invention heavy cycle gas oil fraction of a distillation oil from a mineral oil, preferably a raffinate tion is subjected to the removal of a light distillate, and 0.1 to 10 parts by weight, those below 350 ° at atmospheric pressure percent, based on the weight of the mineral oil, boil. an anti-oxidation hydrogenation product of a 4. A method for producing an insulating oil 30 having a density between 0.99 and 1.10 at 15 ° C, one according to claim 2 or 3, characterized in, viscosity of 2 to 8 cSt at 98.9 ° C, an aniline point that the heavy gas oil fraction of the order of 25 to 80 and one is dewaxed into mineral oil before it is added. . Distillation range from 180 to 66O ⁰ C at atmospheric 5. A process for the production of an insulating oil having heavy cycle gas oil with high pressure.
according to one of claims 2 to 4, characterized by the hydrogenation of the heavy cycle gas oil, that as an additive to the mineral oil a sulfur and oxygen compounds are used, which removes and removes the unsaturated constituents beforehand. The oil obtained in this way is very stable and shows that the components have been enriched. low tendency to form sludge without . 6. Method of Making Insulating Oil 40 Any other properties necessary for Transnach one of claims 2 to 5, characterized by the need for identification formator oils, deteriorated in this case records that the heavy gas oil fraction would have been before hers. The comparison addition below to mineral oil is treated with acid. Tables show the result of the new transformer oil Technical progress achieved, in particular with regard to the acid number and the tangent of the electrical loss angle.
The in the context of the invention as a starting product . heavy cycle gas oil fraction used is in the petroleum refinery in cracking processes, e.g. B. at the 50 catalytic fluidized bed cleavage, won. at these processes develop in addition to the easy ones Products also contain heavy fractions that are in The invention relates to the technology used as insulating oils as "light circulating gas oil" and "heavy Mineral oil mixtures, which, among other beneficial properties, are referred to as “cycle gas oil”. These factions Adhere to an exceptional properties Oxy- 55 are very rich in aromatics and very resistant to heat exhibit. It also affects constantly. Invention a method for. Production of these In general, the characteristics of this fraction lie Insulating oils. within the following limits: It is known to consist of a mineral oil and insulating oils to produce an oxidation-resistant additive. 60 , _ "_ _{,, 3 n} ... ,, _{1 1ΛΛ}
^{According to the} invention, there is this additive, which in Dlchte * ™ ^{15 C} ' Si ™ ³ · ■ 0.990 to 1.100
Amounts of 0.1 to 10 weight percent, based on viscosity at 98.9 ⁰ C, cSt 2 to 8
the mineral oil employed is derived from a hydrogenation product of a heavy cycle gas oil. Here- aniline point, ⁰ C 25 to 80 through are oil mixtures with a high content of 65 distillation range, ° C .. between 180 and 660 Aromatics won. · One already has special fractions ejnes (temperatures converted to atmospheric naphthenic crude oil, which is pressurized by distillation)