CS219178B1 - A method of producing very hard honest bitumens - Google Patents

Abstract

Method for producing very hard honest bitumens with a penetration range of 10-20 penetration units at 25 °C, suitable as a binder for cast asphalt treatments directly by air oxidation at temperatures of 220 °C to 300 °C from paraffinic crudes without the need to use natural asphalt as a recombining component. In the production of very hard honest bitumens according to the above invention, raw materials of optimal chemical group composition are used, in which the ratio of individual chemical groups ranges from ρ + N Ρ + N — ■■■ 1.9 - 3.0 and — o.52 - 0.75 AS ART where P is the content of paraffinic, N the content of naphthenic, AS asphaltenic and ART heavy aromatic hydrocarbons. Optimization of the composition of raw materials allows the use of less valuable refinery products such as, for example, propane asphalt, extracts from selective refining of motor oils. The invention can be used for honest and industrial construction and the paint industry.

Description

3 219178

BACKGROUND OF THE INVENTION The present invention relates to the production of very hard honest bitumen penetration ranges of 10-20 foam units at 25 ° C, suitable as a cast asphalt treatment by air oxidation at temperatures of 220 ° C to 300 ° C, for roads and flats predominantly static. The invention is advantageous to use in the processing of paraffinic petroleum of the West Siberian regions, possibly petroleum containing its portions.

Very hard bitumens for cast asphalts designed for predominantly static load areas showing penetration at 25 ° C 10-20 penetration units, wetting points KG 67 ° C to 80 ° C, body darkness at ± 0 ° C and ductility at 25 ° C up to 5 cm. From the colloid-chemical point of view, these are bitumen with a gel structure depleted in the maltenic structure, enriched in asphaltenes.

Floods were used for the preparation of bituminous hard bituminous crude, rich in bituminous particles with a high asphalt content. These bitumens were able to produce hard bituminous-vacuum, eventually atmospheric distillation (Table 1).

Table 1 Relationship between the outlet temperature furnace and the properties of the obtained bitumen from nagylengyelropy (bitumen yield approx. 50% wt) under 40 torr vacuum (Acid: Bi-thúmen, 1964 Leipzig) Output temperature / ° C 280 320 330 340 388 Properties bituminous penetration / 25 ° C 223 74 33 15 12 wetting point KG (° C) 42 53 65 76 85 A gradual replacement of bitumen oil was required as a result of the rapid depletion of asphalt oil stocks and the necessity to cover the sharp increase in bitumen consumption. These conventional paraffinic feeders are characterized by lower bitumen content, higher paraffinic hydrocarbon content and lower asphaltenes content.

In contrast to asphaltic oils, only bitter bituminous bitumen could be produced by vacuum distillation, with a penetration range of 70-100 penetration units at 25 ° C being the hardest honest bitumen that can be obtained from conventional types of vacuum distillation plants (Table 2). ).

Table 2 Relationship between the outlet temperature furnace and the quality of the obtained bitumen from Soviet commercial grade (bitumen yield 19.5% wt) under 40 torr vacuum Output temperature / ° C 375 385 395 410 bitumen properties: penetration / 25 ° C 400 200 80 68 point the high pressure distillation (1-5 torr) of the vacuum column has not met the expected promise because this high-performance system is as precise as the technological parameters. Furthermore, it is known that by vacuum distillation, either under normal or low vacuum, bitumen can be obtained only in an amount and in a quality which corresponds to the properties of the starting feedstock. Therefore, it is not possible to modify the properties, or the bitumen load. Due to the inevitable need for large hard bituminous bituminous bitumen production, the exclusive recombinant component manufacturing process, with a soft honing bitumen batch produced by vacuum distillation, added asphalt concentrate. For this purpose, predominantly natural asphalt is used (Trinidat containing 26 wt% asphaltenes, Albanian Selenica containing 46 wt% asphaltenes), or other asphaltenic concentrates obtained by extraction processes. In the recombination of the drier honest vacuum bitumens, the asphaltenes act as a filler, thereby increasing the dipping, decreasing the ductility (ductility) of the point of penetration (Table 3).

Table 3 Change in the properties of the A-80 distillation bit and the AP-65 semi-blown bit-bit by the addition of Albanian natural asphalt Selenium Initial bitumen A -80 AP —65 addition Selenium% wt 30 40 50 20 30 40 properties: wetting point KG / ° C 63 72 78 63 68 77 penetration / 25 ° Cductility / 25 ° C 21 14 12 22 16 10 / cm 18 7.5 4 21 9 3.5 point breaking / ° C ± 0 +2 +4 ± 0 +2 +4

It has been shown that the use of conventional asphaltic oils as well as the recombination of the more dense paraffinic bituminous bitumen with asphaltenic concentrates can be ruled out in the hard bituminous bitumen penetration grades, 10-20 penetration units, if they are oxidized by air at temperatures of 220 ° C up to 300 ° C vacuum distillation residue, a mixture of vacuum residues, a mixture of vacuum residues and less valuable refinery products if these correspond to a precisely defined chemical composition. 4 219178

The chemical group composition of the oxidizing feedstock must correspond to a precisely defined ratio of the individual chemical components that will exert a significant influence during the oxidation. These are the ratio of paraffinic and naphthenic hydrocarbons (P + N) to the content of asphaltenes (AS) and at the same time to heavy aromatic hydrocarbons (ART).

SUMMARY OF THE INVENTION The present invention is based on the oxidation of a vacuum residue, a mixture of vacuum residues, or a blend of residuals with less valuable byproducts such as bitumen from propane deasphalting, extracts from the refining of lubricating oils, in which the individual chemical constituents range

P + NAS <1.9-3.0>

P + NART <0.52—0.75> where P - is the content of paraffinic hydrocarbonsN - is the content of naphthenic hydrocarbonsAS - is the content of asphaltenes ART - is the content of heavy aromatic hydrocarbons. Advantages of using the present invention include the possibility of replacing conventional asphaltic paraffinic petroleum crude oil, substituting paraffinic distillation residues for paraffinic distillation residues, or mixtures thereof in the production of high-strength honest bitumens of 10-20 penetration units at 25 ° C.

A further advantage of the use is the efficient use of less valuable refinery feedstocks than bitumen from propane deasphalting, extracts from the selective refining of lubricating oils, thereby achieving, in addition to their effective use, an increase in the yield of bitumen product, especially in the case of paraffinic oils. lower bitumen content. Examples

The composition and chemical group composition of the individual raw materials are shown in Tab. No. 4.

Raw material No. 1.

A mixture of 90% by weight of a vacuum residue of 390 ° C / 25 ° C and a wetting point of KG 35 ° C and 10% of a paraffinic extract of type designation E 353 - P viscosity of 17.78 mm 2 / with 100 ° C of selective oil refining whose ratio individual chemic-

The P + N P + N groups are - 3,11a - = 0,78 are oxidized at 270 ° C to a bitumen of penetration gradation of 10-20 penetration units at 25 ° C. The bitumen exhibited the following properties: penetration / 25 ° wetting point 10 12 15 18 20 KG / ° C 87 84 81 77 74 ductility / 25 ° C / cm 0 0 0 2 3 breaking point / ° C -8 -10 -11 -13 It is clear from the aforementioned Quality Overview that in the penetration area of 10-20 pounds. The bitumen produced at 25 ° C does not cover the entire desired range of spraying points of 67 ° C to 80 ° C, but substantial higher values are obtained. The high content of paraffins and naphthenes as well as the low content of components that preferentially participate in oxidation as heavy aromatic hydrocarbon asphaltenes, the composition of the raw material deviates from the optimum composition. The resulting product has a higher content of paraffinic and naphthenic constituents, as compared to the content of asphaltenes, which indicate a higher level of wetting, a higher content of light aromatic lower content of heavy aromatics. As a result, the product shows favorable swelling points.

Raw material No. 2

A mixture of 70% vacuum penetration / 25 ° C 390, KG 35 ° C and 30% non-paraffinic extract of E 353 N viscosity 14.45 mm 2 / s 100 ° C has a ratio of

P + N P + N chemical groups - = 3.22 and - =

AS ART = 0.52, thus satisfying the optimal composition.

By oxidation with air at a temperature of 270 ° C, a bitumen of the following properties is obtained in the penetration zone of 10-20 penetration units at 25 ° C: penetration / 25 ° C 10 12 15 18 20 dipping point KG / ° C 79.5 77 72.5 69 67 ductility / 25 ° C / cm 0 1 4 10 14 breaking point / ° C ± 0 -1 —2 -3 —4 The prepared bitumen corresponds to the quality parameter required for hard honest bitumen.

Raw material No. 3 Vacuum distillation residue of 390 pellet units at 25 ° C and a soak point KG of 35 ° C, whose ratio of individual

P + N P -h of the N-groups is-= 2.87 and - = 0.75 sec

JH J AS ART oxidizes at a temperature of 270 ° C to the 10-20 penetration penetration bitumen. units at 25 ° C.Bitman exhibits the following properties: penetration / 25 ° Clogging point 10 12 15 18 20 KG / ° C 81 79 76 73 71 ductility / 25 ° C / cm 0 0 2 6 8.5 breaking point / ° C —4 -5 —6 -8 -9 5 i · 219178

The oxidation raw material, by its chemical composition, forms the optimum composition of the ingredients, which is also indicated by the quality of the product obtained in the entire penetration width of the gradation. spraying point KG / ° C 69.5 68 65.5 63 ductility / 25 ° C / cm 0 3 13 40 breaking point / ° C 0 -1 —2 —4

Raw material No. 4

A mixture of 85% vacuum penetration residue / 25 ° C 390, KG 35 ° C and 15% hmpropane penetration / 25 ° C 33, KG 53 ° C has a chemical ratio of

P + N P + N groups -? = 1.91 and - = 0.57, thus meeting the optimum requirements of AS ART 7. By oxidizing the temperature of 270 ° C, a bitumen of the following properties is obtained in the penetration area of 10-20 penetration units at 25 ° C:

The chemical group composition as well as the ratio of the individual groups that play a decisive role in the oxidation process, to the fact that the feedstock due to the higher content of phthalenes and heavy aromatics does not correspond to the optimal group composition. In the penetration range of 10-20 penetration units at 25 ° C, the bitumen exhibits lower dipping points as prescribed qualitatively by the requirements. Due to the low content of paraffins in the product, ductility increases. penetration / 25 ° point of wetting 10 12 15 18 20 KG / ° C 73 72,5 70 68,5 67,5 ductility / 25 ° C / cm O; 1 5 8 13 breaking point / ° C ± 0 -1 -1.5 -2.5 —3

Raw material No. 6

The mixture of feedstock to suit the optimum chemical composition provides a product of suitable properties.

A mixture of 50 wt% vacuum penetration residue / 25 ° C 72 penetration point penetration units KG 48 ° C and 50 wt% vacuum penetration residue / 25 ° C 390 and dipping point 35 ° C corresponds to the chemical composition of the ratio groups

P + NAS

P + N 1.95 and-= 0.56,

ART J

Raw material No. 5 Vacuum distillation residue / 25 ° C72 units of soaking point KG 49 ° C, in which the chemical group composition corresponds to

P + NAS = 1.44 and -0 = 0.41 was oxidized by air

ART chom at 270 ° C. In the penetration area of 10 - 20 penetration units at 25 ° C, the following properties are obtained: penetration / 25 ° C 10 12 15 18 20 is the optimum composition.

By oxidation at 270 ° C, the following properties are obtained in the penetration area of 10-20 penetration units at 25 ° C: penetration / 25 ° wetting point 10 12 15 18 20 KG ° C 74.5 73 71 69 68 ductility / 25 ° C cm 0 1 4 7 8 breaking point ° C ± 0 -1 —2 -3 — 4

The product produced, due to the optimal raw material composition, meets the quality requirements throughout the penetration area. and

Table 4 Properties and chemical group composition of raw materials used

Raw material No. Composition Paraffin and naphthaleneP + N% wt AsphaltenesAS% wt Light and medium aromaticsARLS% wt áty Heavy mortarART% wt P + N AS P + N ART 1. 90 wt% vacuum penetration residue / 25 ° C, 390 , wetting point KG 35 ° C 10% paraffin extractE 353 P viscosity 17.78mm 2 / s 100 ° C 17.5 5.63 / 54.44 22.43 3.11, 0.78 2. 70 wt. penetration residue / 25 ° C390, wetting point KG 35 ° C 30% non-paraffinic extract E 353 N viscosity14 ·, 45 mm2 / s 100 ° C 13.08 4.06 57.80 25.06 3.22 0, 52

Claims (1)

6 219178 Continued tab. No. 4 Raw material No. Composition Paraffin and naphthaleneP + N% wt AsphaltenesAS% wt Light and medium aromaticsARLS% wt Ť Heavy weightMartart% wt P + N AS P + N ART 3. 10 (0 wt% vacuum penetration 25 ° C39 °, wetting point KG 35 ° C 17.62 6.13 52.75 23.5 2.87 0.75 4. 85% w / w vacuum dist. Penetration / 25 ° C390, wetting point KG 35 ° C 15 % wt propane bitumen penetration / 25 ° C 33, wetting point KG 53 ° C 14.68 7.7 52.03 25.59 1.91 0.57 5. 100 wt% vacuum penetration residue / 25 ° C72, wetting point KG 48 ° C 11.06 11.7 49.93 27.37 0.95 0.40 6. 50% w / w vacuum dist. Penetration / 25 ° C72, wetting point KG 48 ° C 50% w / w vacuum penetration residue / 25 ° C390, wetting point 35 ° C 14,34 7,36 52,9, 25,4 Λ'λ · + -1 1,95 0,56 Very hard penetrant penetration The 10-20 penetration units at 25 ° C prepared according to the present invention are advantageously used as a binder for road and flat applications. urban traffic, car parks, urban public transport stops and floors of industrial, agricultural and other objects. Bitumen produced by the above-mentioned technology can also be used in the manufacture of bituminous ethers and other areas of construction, where the bitumen of said penetration range is required. OBJECT OF THE INVENTION A method for producing very hard honest bitumen penetration ranges of 10 to 20 penetration units at 25 ° C, suitable as a binder for spraying asphalt treatment by oxidation with air at temperatures of 220 to 300 ° C, characterized in that the distillation residue is used, the mixture of vacuum distillation residues, or a mixture of vacuum distillation residues with less valuable refining products such as extracts of refined oil refining, propane bitumen and the like, whose chemical composition is expressed by the total content of paraffinic (P), naphthenic (N) hydrocarbons, asphaltenes (AS) and Heavy Aromatic Hydrocarbons (ART) correspond to P + NAS P + LOAD <1.9—3.0> <0.52—0.75>