CS208333B1 - A method for recovering worn hydrocarbon mixtures - Google Patents

Abstract

The invention "Method of regeneration of hydrocarbon mixtures" solves the problem of regeneration of worn hydrocarbon mixtures so that they return to their original properties. The essence of the invention is a method of regeneration of decarbonized hydrocarbon mixtures based on the deethylation of the mixture into hot fractions up to 360 °C, into oil fractions with a viscosity at 100 °C of up to 25 mm2/s and a vacuum residue. The oil fractions are hydrogenated and the vacuum residue is extracted with propane and subsequently hydrogenated. For the purpose of better function of the extraction column and the vacuum residue, it can be mixed with extraction asphalt, then extracted with propane and then hydrogenated. Products after hydrogenation can still be refined with absorbent clay. The invention can be used in the field of processing oil and oil products.

Description

The invention "Method for Regeneration of Hydrocarbon Mixtures" solves the problem of regenerating worn-out hydrocarbon mixtures so that their original properties are restored.

The essence of the invention is a method for the regeneration of decarbonized hydrocarbon mixtures based on the diethylation of the mixture into fractions boiling up to 360 °C, into oil fractions with a viscosity at 100 °C up to 25 mm ² /s and a vacuum residue. The oil fractions are hydrogenated and the vacuum residue is extracted with propane and subsequently hydrogenated. For the purpose of better functioning of the extraction column, the vacuum residue can be mixed with extraction asphalt, then extracted with propane and subsequently hydrogenated. The products after hydrogenation can be further refined with absorbent clay.

The invention can be used in the field of processing oil and oil products.

208,333

208,333

The invention relates to a method for the regeneration of spent hydrocarbon mixtures, e.g. spent mineral oils, or their parts, pre-purified to the level required for optimal catalyst life in the subsequent hydrorefining process, which may be supplemented by further refining with clay.

In all industrial sectors, various hydrocarbon mixtures are used for lubrication, a significant part of which is mineral oils. These hydrocarbons are subject to aging and thermal decomposition under operating conditions and are contaminated in various ways. When they reach a certain degree of contamination, they must be replaced, and when worn out, they are often used as ballast for which they are not suitable. Inappropriate use of these substances for emergency purposes, or their discharge into industrial waste dumps, can lead to ecological damage to the country and thus to environmental degradation.

Also, the burning of spent hydrocarbon mixtures is considered inefficient and is prohibited by law in some countries. Society has an interest in protecting the environment and in the efficient disposal of this waste. Therefore, spent hydrocarbon mixtures are collected and regenerated. The interest of society requires collecting the maximum amount of used hydrocarbon mixtures and regenerating them. However, current regeneration technologies are either too expensive or not efficient enough.

Currently, the following technologies are known in the world for the regeneration of used hydrocarbon mixtures:

1/ Refining with sulfuric acid - this process is still the most prevalent on a global scale. The products obtained by regenerating sulfuric acid are of high quality, but the disadvantage of this process is the formation of aggressive acidic wastes that pollute the environment. The yields of these processes are about 75%.

2/ Liquid propane extraction - processes are described in the literature

Dang Vu Quang and others: Hydraoorbon Prooessing no. 12, 1976 p. 130 - 131 E.T. Outler, Hydrocarbon Processing no. 5, 1976 p. 86 *

L. Bolton, Chem ool Eh£ineering, July 3, 1978, 20 o K, Staege and lni, Sohmierungsteohnlk No. 10, 1973 p, 302

3/ Extraction with a mixture of propane, butane and ammonia Pat. 80503 NSR.

4/ Contact with sodium metal - the process is described in Tribology International, October 1978, p. 306

The disadvantage of this process is the difficult handling of metallic sodium.

The disadvantages of the above processes are the generation of difficult waste, high energy requirements, corrosion of production equipment, low performance and short catalyst life.

The above-mentioned shortcomings can be eliminated by using the technology according to the invention, which consists of decarbonizing the processed hydrocarbon mixtures with a solution of alkali metal silicates with a density of 1.035 kg/m** to 1.356 kg/m^ (5° Bé to 38° Bé)

208 333 in an amount of 0.1% by weight to 4% by weight at a temperature of 10 °C to 100 °C with a possible addition of ethyl alcohol in an amount of 0.05% by weight to 2% by weight. From the obtained decarbonized oil, the fractions with a boiling point of up to 360 °C are distilled off, the residue is vacuum distilled into oil fractions and a vacuum residue. The oil fractions are hydrogenated and the vacuum residue is extracted with propane and hydrogenated.

Extraction is carried out at temperatures of 50 to 96 °C, at a mass ratio of propane to oil of 3:1 to 10:1 and a pressure of 3 to 4.3 MPa, or in order to facilitate the removal of cured impurities from the reactor, the vacuum residue is mixed with extraction asphalt, e.g. propane asphalt, and then extracted under the above conditions.

Hydrogenation of oil fractions and the residue after extraction is carried out under the following conditions: temperature from 200 °C to 400 °C, space velocity from 0.5 nP/nPh to 3 m^/m^h and hydrogen vapor pressure from 2.5 MPa to 7 MPa.

If necessary, the products after hydrogenation can be further refined with adsorption clay at temperatures from 60 °C to 250 °C,

The process is characterized by a high yield of regenerate. This is made possible by combining complete decarbonization with subsequent processes. The advantage of the process according to the invention is that it does not require the entire amount of decarbonized oil to be processed in a propane extraction, but only the residue after vacuum distillation.

Example of design:

Used engine oil was regenerated using the process of the invention under the following operating conditions:

Decarbonization:

Example 1:

The oil, freed from coarse mechanochemical impurities and water by sedimentation, was heated to a temperature of 80 °C, and 1.6% by weight of a solution of alkali metal silicates (water glass) with a density of 1319 kg/nP (35° Bé) was added while stirring. After thorough mixing, the oil was allowed to settle at a temperature of 80 °C. By sedimentation, the mixture was divided into a lower layer, in which there was a chromite carbene coagulum, and a decarbonized oil in the upper layer.

Example 1a:

This decarbonization procedure differs from example 1 only in that 1.0% by mass was added simultaneously with the addition of the alkali metal silicate solution. ethyl alcohol.

The properties of the original used oil and the properties of the oil after decarbonization according to Examples 1 and 1a are in Table S. 1.

208,333

Table 8. 1

Spent oil after removal of coarse meeh.neé. and water After decarbonization After distillation of the fractions heated to 360 °C Example 1 Example 1a Viscosity 50 °0, mm ² /s 35.82 33.64 33.72 51.02 Viscosity 100 °0, mm ² /s 7,781 7,326 7,341 9,752 Viscosity index 103 98 99 95 Freezing point °C -36 -36 -32 -30 Flash point °C PM 116 120 124 160 Flash point °0 0T 130 130 126 182 COT, % wt. 1.31· 0.37 0.33 0.43 Ash, wt.% 0.52 0.15 0.16 0.17 Color 8th grade Stern theme Siem Reap

From Table 8.1 it can be seen that the efficiency of decarbonization with the addition of ethyl alcohol is the same as without the addition, therefore the following technological operations were performed only with oil processed according to Example 1.

Distillation:

After separation of the lower coagulum layer formed by decarbonization, the fractions were distilled from the upper oil layer at atmospheric pressure at temperatures up to 360 °C and the residue was vacuum distilled. The properties of the oil after distillation of the fractions up to 360 ^° C are given in Table 8.1, and the properties of the vacuum distillates and the vacuum residue are given in Table 8.2.

Table 8. 2 Properties of vacuum distillates and distillation residue

1st class 2nd class ^r dist. residue Viscosity 50 °C, mm ² /s 32.82 64.04 • Viscosity 100 °C, mm ² /s 6,941 10.75 34.75 Viscosity index 86 78 Freezing point °C -18 -i4 Flash point °0 202 228 284 CCT, wt.% 0.17 0.22 3.68 Ash, $ wt. 0.007 0.007 0.72 Color 4.5 ISO 5.5 ISO black Yield ^x , wt.% 40 35 25

^x Yield per atmospheric residue

The vacuum distillates were hydrogenated and refined with clay, the vacuum distillate residue was extracted with propane, hydrogenated and refined with clay. Hydrogenation and refining of the still and vacuum residue were carried out under the same conditions.

Operating conditions1 propane extraction: column temperature - top CS °0 - bottom 75 °C

208 333 column pressure 3.8 MPa oil to propene ratio 1 : 7 hydrogen: reactor temperature 370 °C water vapor pressure 4.8 MPa space velocity 1 m^/m^h clay finishing: temperature 150 °C clay amount 3.0 wt. %

The properties of the vacuum residue after extraction with propane, hydrogenation and further refining with clay are in Table δ. 3. The properties of the distillates after hydrogenation are in Table δ. 4 and after further refining with clay in Table δ. 5

Table δ. 3 Properties of vacuum bottom residue after extraction with propane, hydrogenation and further refined clay

After extraction with propane After hydrogonation After refining with clay Viscosity 50 °C mm ² /s 206.1 212.4 202.09 - - 100 °C mm ² /s 23.92 25.12 24.41 Viscosity Index 77 ⁸² 84 Freezing point, °C -8 -4 -6 ; Flash point °c I 262 270 272 CCT, # wt. ; 0.89 0.56 0.45 Ash, $ wt. 0.04 0.008 0.008 ISO color 8 6.. 4 ^weight, % wt. 82 79 76

^x Yield per vacuum distillation residue

Table δ. 4 Properties of distillates after hydrogenation (after stripping of hot components up to 360 °C)

1st class 2, Frakoia I Viscosity 50 °C mm ² /s 36.18 56.90 - - 100 °C mm ² /s 1 7,511 10.04 : Viscosity index 90 83 í Freezing point °C -12 -10 ' Flash point °C 214 224 : CCT, $ wt. 0.08 0.11 ! Ash, eats matter. 0.004 0.006 : Color according to ISO 2.5 3.5 1 ^x Yield, # wt. 37.5 33.0

^x Discharge to atmospheric residue

208,333

Table 8. 5 Properties of hydrogen diethylates after clay refining

1, fracoia 2nd class Viscosity 50 °C mm ² /· 34.62 54.45 Viscosity 100 °C mm ² /s 7,320 9,854 Viscosity Index 92 86 Freezing point °0 -14 -10 Flash point °C 218 226 COT, $ wt. 0.06 0.09 Ash, wt.% 0.004 0.004 ISO certification 2.0 2.5 ^X Yield, wt.% 35.3 31.4

Atmospheric noise yield

The following complete oils were prepared from the hydrogenated oils obtained by the process according to the invention:

- from frakoie δ, 1 by adding 1.7 5% complex additive and 0.5% mass, freezing point depressant, automotive oil M4A under ČSN 65 6638

- from fraction 8. 2 by adding 1.7% by mass, complex additive and 0.5% by mass, depressant of the freezing point, automotive oil MÓA according to ČSN 65 6638

- usually by mixing with fresh, previously unused hydrogenate in a ratio of 7:3 and adding 0.1% by weight of a pour point depressant, durable compressor oil K 18 according to

ČSN 65 6650

From Table 8.6, which includes the requirements of the relevant ČSN for the quality and properties of the prepared oils, it can be seen that all 3 oils fully meet the required criteria.

From the oils which were further refined with clay after hydrogenation, oils of the same composition as from the hydrogenated oils were prepared. The results are summarized in Table 8.7. From this table it can be seen that these oils also fully meet the required criteria.

208 333 what

B *

8 &

TJ A ® fa r4

O N

CM 4# what what -4 CM *. 3· -cr -4 About about CM CM About VO •to WHAT in about «» M VO In" CM 1 Sk About 00 In T· OJ about

•at

Φ about

\o 4» o 'fl o“ & 8 cm vn o cn

About

Ό W VO >O vn

VO

About

r. ον o ό co * ·» τ- t- CO CM | O O o ΤΓ other ▼ ·» o v·

Pr I g

«P

P ° 5 i

S oa & fa k 8 ^ft & TJ m

Φ fa o a

Ov 00 00 yes 00 about in Ov cn •to 00 cvt CM cn T· OV in m About CVJ 1 •to •to •to In about About in about -4·

g

4J

Table δ. 6 Properties of complete oils prepared from hydrogenates

XJ what is it

VO

VO

1Π

VO a >: t § & & •o φ Φ H O K co cn

Oh

Ό >o vn vo

O o o vn » cn

N 1Λ N Ol - «

- CO N | O O r4 ní

Ov vn vn - - o vo

S * 9 ® o 9/>

CM

1 in 00 yes VO Γ* CM in cn in In" CM CM T· CM cn in •to of CM 1 «k «k •to «k WHAT About about VO about <ň

about vn vn vn *· cm

Ov O * CM * ♦*

Ο» CM I O O o *

T-o m

r•ss.

about

4>

§

H ti m · i * rM cn g.

»» cd

Φ About ftfi

’.?mí ec .0 «0 * jl %! μ and xo <ď

208,333

Properties of complete oils prepared from hydrogenates refined with clay

208,333

Example 2

This procedure is completely identical to the procedure of Example 1 in the decarbonization part and the distillation and treatment of the still, including its finalization, are also identical, but the method of processing the vacuum distillation residue is different. In the procedure of Example 2, the vacuum distillation residue was mixed in a weight ratio of 1:1 with propane asphalt and this mixture was extracted with propane and subsequently hydrogenated under the same conditions as those given in Example 1.

The advantage of this process is that propane asphalt acts as an adsorber and remover of residual metal additives and increases the amount of extract phase with its volume, which has a positive effect on the uniform flow of the extraction column.

The properties of the propane asphalt used were as follows:

penetration at 25 °C 31 Drip point KG °C 54°C breaking point °C +1°C ductility at 25 °C 100 ash content 0.08 ;

The yields and properties of the distillation residue are given in Table 8.

Table No. 8 Properties of the vacuum distillation residue after extraction with propane, hydrogen oil and refined clay

After extraction with propane After hydrogenation 1 • •1 After paraffining with clay i í Viscosity 50 °C mm?/s 185.4 204.3 ! < í 192.3 - - 100 °C mm^/s 22.05 24.11 23.22 Viscosity index 75 80 81 Freezing point °C. -10 -6 -8 Flash point °C 266 27Ο 274 CCT % wt. 0.80 0.51 0.46 Ash $ wt. 0.03 0.007 0.007 Color according to ISO 8 6 4 days ^x Yield of IH mass. 75 72 70

^x Yield on vacuum distillation residue

From the hydrogenated vacuum residue and the vacuum residue, which after hydrogenation was further refined with clay, compressor oils £ 18 were prepared according to ČSN 65 6650. The composition of the oils and their properties are in Table No. 9.

208,333

Table δ. 9

fresh, unused hydrogenate hydrogenated vacuum residue - - - - - - - do- clay-refined pour point depressant 30% wt. 70 wt. 0.1 her mass. 30% wt. 70 1» mass. $0.1 wt. Viscosity 50 °0 mm ² /s 170.3 148.7 Viscosity 100 °C mm ² /e 22.06 20.12 Viscosity Index 87 87 Flash point, OT, °C 268 264 Freezing point °0 -10 -10 Ash 1» wt. 0.004 0.004 00T - ash, 1» wt. 0.22 0.20 Oxidative stability 180 °C, 16 hours. - viscosity increase 50 °C by % 8.56 8.15 - increase in CCT by 1.20 0.97 Water pomace reaction neutral neutral Salt acidity mg KOR/g 0.06 0.05 Asphaltans absent absent

Comparing the results given in Table 9 with the requirements of ČSN 65 6650, the properties of compressor oil K 18 show that both oils meet all criteria.

Claims (3)

208 333 9 Table δ. 9 fresh, unused hydrogenated hydrogenated vacuum residue - "- -" - - "- topped with clay pour point depressant 30% by weight 70% by weight 0.1% by weight 30% by weight 70% by weight 0.1 Viakozlta 50 ° 0 mm2 / s 170.3 148.7 Vlakozlta 100 ° C mm2 / a 22.06 20.12 Viscosity Index 87 87 Flash Point, OT, ° C 268 264 Freezing Point 0 0 -10 -10 Ash Weight 0.004 0.004 00T - Ash 0.22 0.20 Oxidity Stability 180 ° C, 16 hrs. - Viscosity Increase 50 ° C% 8.56 8.15 - CCT Increase $ 1.20 0 , 97 Reakoia of water neutral neutral Neutral kyeloati mg KOR / g 0,06 0,05 Asphaltenes absent Absence of comparisons of the abovementioned values in Table No. 9 and requirements of CSN 65 6650 K 18 compressor oil properties According to the invention, the method of regeneration of worn carbon monoxide depletes alkali metal oxides with a solution of cesium silicate, characterized by carbonized carbon monoxide is distilled to fractions with a boiling point up to 360 ° C, for oil fractions and 100 ° C max. 25 mm / a and vacuum residue, oil fractions are catalytic hydrogenated at a temperature of 200 ° C to 400 ° C, vapor pressure hydrogen 2.5 MPa to 7 MPa and at least 0.5 m 2 / m 2 to 3 m 3 / m 2 / h, vacuum residue and extracted with propane at 50 - 96 ° C, with a propene to oil mass ratio of 0.3 1 to 10 t 1 and a pressure of 3 to 4.5 MPa, and hydrogenates in the same conditions as the oil fractions. 2 / Method according to claim 1, characterized in that the vacuum residue aa is mixed with extracorporeal asphalt in a weight ratio of 1 to 3 to 10 1 and extracted with propane and hydrogenated under the conditions as in point 1. 1, or 2, characterized in that the products after hydrogenation and purification by means of an adsorbent clay at a temperature of 60 to 250 ° C.