DE2707158A1 - PROCESS FOR THE PRODUCTION OF PECH-LIKE MASSES - Google Patents

Description

ΡΑΤΖΝΤλ JWXlTc

DR. E. WIEGAND GPL-INO. W. NIEAAANN 2707158

DR. M. KÖHLER DIPL-ING. C. GERNHARDT MÖNCHEN HAMBURG Phone. 55547 «8000 M 0 N CH E N 2, TELEGRAMS: KARPATENT MATHIIDENSTRASSE 12 TELEX: 5 29 048 KARP D "Y * W. 42 793/77 ZiAch 18 February 1977

Mobil Oil Corporation New York, (V.St.A.)

Process for the production of pitch-like

Crowds

The invention "relates to a method of manufacture -of pitch-like masses.

Over the past hundred years, petroleum has become an extremely important organic raw material. It has as Liquid has the advantage of low cost, easy transportation and storage. It can also be simply fractionated and into a variety of products, such as Fuels and fuels and chemical intermediates are converted. However, recent developments have made the petroleum less readily available at an acceptable cost. The price of crude oil is substantial gone up. The verbi-odor of crude oil has also increased significantly and the "known crude oil reserves of the world have therefore decreased considerably. It has therefore now become desirable to use alternatives to petroleum as a raw material for Combustibles and fuels and chemical intermediates too

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Looking for. Coal has often been considered, especially as there are large reserves of coal in a number of Developed countries exist.

Coal can be liquefied by controlled heating in the substantial absence of oxygen, producing a liquid and tar as decomposition products. The technology of liquefaction and Gasification of coal has been improved since pioneering developments such as the Lurgi and Fischer-Tropsch processes.

Other raw materials have also attracted attention as possible substitutes for materials currently in use are obtained from petroleum. For example, there are very large amounts of old rubber in industrialized countries. Although the rubber is largely synthetic and Obtained from petroleum, it is not currently used widely and is disposed of in the form of Waste represents the destruction of valuable material that was originally extracted from petroleum.

It has now been found according to the invention that waste rubber can be converted into synthetic pitch or synthetic Asphalt can be converted by dissolving the waste rubber in by-product streams of the petroleum refinery. Although both materials are derived from petroleum, the synthetic pitch and synthetic asphalt are based on made this way from old material that would otherwise be destroyed. Those made according to the invention Masses can replace the pitch and asphalt masses that are currently made directly from petroleum. Other,

♦) Rubber waste

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Materials not made from petroleum, such as coal or wood, can also be included in the masses in order to further reduce the petroleum content.

The synthetic, pitch-like substances and asphalt masses are produced according to the invention in that a sludge made of crushed old rubber and a thermally stable, extremely heat-resistant petroleum material obtained in a refinery with a 5 boiling point between 232 and 593 ⁰ C (450 and 110O ⁰ P) is formed, and the sludge thus formed is ^{heated to a temperature between 177 and 454 0} C (350 and 850 ° ϊ) for a period of time sufficient to turn the sludge into a homogeneous mass with a pitch-like To convert consistency at temperatures below 93 »3 ° C (200 ⁰ F). The homogeneous mass can then be mixed with asphalt materials to produce an asphalt-forming product.

The thermally stable, extremely heat-resistant crude oil fractions that arise during refining are high-boiling crude oil residues, such as TCC "syntower residues" or FCC "main column residues". They contain substantial amounts of polycyclic, aromatic hydrocarbon components such as naphthalene, dimethylnaphthalene, anthracene, phenanthrene, fluorene, chrysene, pyrene perylene, diphenyl and benzothiophene. These heat-resistant petroleum substances are very resistant to conversion into products of lower molecular weights by conventional, non-hydrogenating processes. These petroleum-refinery residues and return fractions are typical hydrocarbon mixtures having an average carbon ZWasserstoffverhältnis above about 1: 1 and tinea 5 # strength boiling point above 232 ⁰ C (45O ⁰ F), preferably above 316 ⁰ O (60O ⁰ F) or even 343 ⁰ C (65O ⁰ F).

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The petroleum solvents suitable for the invention are thermally stable, highly polycyclic, aromatic Mixtures resulting from one or more refining processes for petroleum. Examples of severe Petroleum solvents are syntower residues, main pillars residues, coker gas oil, heavy return oil, clarified oil and mixtures thereof.

The nominal properties for some examples of suitable petroleum solvents are as follows:

Syntower residues sulfur 1.13 96 nitrogen 450 ppm Pour point 10 ⁰ C (50 ⁰ F) 5% boiling point 338 ⁰ C (64O ⁰ F) 95 # boiling point 485 ⁰ C (905 ⁰ F) Conradson carbon 9.96

Clarified mud oil

Sulfur 1.04 %

Nitrogen 4400 ppm

Pour point 10 ⁰ C (50 ⁰ F)

5 # boiling point 332 ⁰ C (63O ⁰ F)

95 iger boiling point 495.5 ⁰ C (924 ⁰ F)

Conradson Carbon 10.15

Heavy Return Oil Sulfur 1.12 #

Nitrogen 420 ppm

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5 # boiling point 232 ⁰ C (45O ⁰ F) 95% boiling point 40O ⁰ C (752 ⁰ F) Conradson carbon 10.15

A refined fraction of FCC main column residue or TCC syntower residue is an extremely preferred one Solvent. The term "syntower residue" denotes a residue product that is produced by product fractionation the TCC process (Thermofor Catalytic Cracking). The term "main column residue" refers to a residue product that consists of the product fractionation of an FCC process (fluid Catalytic cracking) is obtained. The catalytic fines can be separated from the residues before they are used.

A typical FCC main column residue contains a mixture of chemical components with the following epectrometric analysis:

links Aromatics Naphthenes /
Aromatics more unstable
hydrogen Alkylbenzene
Naphthenobenzenes
Dinaphthenobenzenes 0.4 1.0
3.7 0
0.03
0.16 naphthalene
Acenaphthenes (biphenyls)
Fluorenes 0.1 7.4
10.1 0
0.08
0.11

Phenanthrenes 13.1 Naphthenphenanthrenes 11.0 0.18

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Pyrene, Fluoranthene 20.5 Chrysene 10.4 Benzofluoranthenes 6.9 Perylenes 5.2 Benzothiophenes 2.4 Dibenzothiophenes 5.4 Naphthobenzothiophenes

ο ο

0 0

2.4 0.04 total 64.4 35.6 0.60

A typical FCC main column residue has the following nominal analysis and properties:

Elementaran alyse wt -.%

C. β together 89.93 H 7.35 0 0.99 H 0.44 S. 1.09 99.80

Flow point IQ ⁰ C (50 ⁰ P) Conradson Carbon (CCR) %: 9.96

Distillation IBP 254 ⁰ C (490 ⁰ P) 5 * 338 ⁰ C (64O ⁰ F) 95 * 485 ⁰ C (905 ⁰ F)

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A preferred FCC main column residue is achieved by depositing the product, the cooking grass oil is obtained in the presence of a solid, porous catalyst by the catalytic cracking of an 343 ⁰ C (65O F ^0). The production of this petroleum fraction is described in more detail in US Pat. No. 3,725,240.

The crushed old rubber, which is mixed with the petroleum solvent, is preferably a natural or synthetic hydrocarbon rubber. These Rubbers are generally asphalt-soluble and not oil-resistant and can either be vulcanized or unvulcanized, while it is possible to be new and unused To use elastomeric materials as rubber components for the compositions according to the invention, it is particularly advantageous to use old rubber or regenerated rubber for reasons of economy and environmental protection. The expression "old rubber" used earlier also includes "regenerated" rubber or "regenerated rubber" and "rubber waste" «

Suitable rubbers are, for example, natural rubber, isoprene rubber, butadiene rubber, butadiene-styrene rubber, butyl rubber and ethylene propylene rubber. The rubber component can, for example in the form of a whole, ground rubber tire with or without carcass fibers, unprocessed rubber waste, as they arise, for example, when retreading tires, ground tire hoses, regenerated rubber or partially devulcanized, regenerated rubber are present »

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The reclaimed rubber can be de-vulcanized or partially devulcanized and made by the digester process, heater or ladle process, Lancaster-Banbury process, and other conventional regenerative processes described in U.S. Patent 3,891,585 are described.

All tire rubber can be ground, sifted, cleaned and treated to remove metal, Remove cord and fabric. However, all of the tire carcasses used are shredded and without any further Treatment used directly.

The component of the crushed waste rubber can in the form of a fine powder with a particle size between: see 40 and 200 mesh (US standard - 0.42mm to 0.074mm Mesh size) are introduced into the reaction system. A process for the production of finely powdered waste rubber is described in US Pat. No. 2,853,742. It is It is also useful and practical to use the old rubber in the form of a frayed or chopped material. The particle size of the rubber cubes or pieces of rubber can be between 1.27 and 12.7 mm (0.05 and 0.5 inch) lie.

The component of the thermally stable petroleum solvent acts like a solvent to dissolve the old rubber. The petroleum solvent and waste rubber components are mixed together to form a sludge. The slurry thus formed is heated to a temperature of 177-454 ⁰ C (350 and 85O ⁰ F), preferably 260-427 ⁰ C (500 and 800 ⁰ F).

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The procedure can be in an open or closed System under moderate or high pressures.

The slurry is heated for a period of time sufficient to achieve a mass that remains homogeneous after cooling to ambient temperature, and a pitch-like or semi-flowing consistency at temperatures below the freezing point to has to 93.3 ⁰ C (20O ⁰ F). The mass can therefore be used as a sealing material. The heating process of the method is carried out over a period of time between 0.2 and 3 hours, preferably between 0.5 and 1.3 hours.

The amount of the petroleum solvent component in the solution mixture is between 0.5 and 50 parts by weight per part by weight of the component of the waste rubber. The preferred amount is usually between 1 and 20 parts by weight of petroleum solvent per part by weight of waste rubber. Typical compositions contain between 5 and 30% by weight of rubber.

The process can produce a wide variety of rubberized, pitch-type caulks and asphalt compounds.

The pitch compounds have excellent elasticity and excellent adhesiveness over a wide temperature range, which extends, for example, from -28.9 to + 93t3 ° C (-20 ⁰ F to + 200 ⁰ F). These compounds are suitable for sealing materials, casings for pipelines, impregnation connections, connections for lining pipelines and for the production of roofing felt and insulating materials. They are also suitable for the production of wet asphalt.

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A particularly excellent type of asphalt compound can be produced by using waste rubber, such as described above, heated and dissolved in petroleum solvent and mixed with the homogeneous mass, so that an asphalt material is made from coal, solvent-refined coal, petroleum or wood. For example, a petroleum tar such as a propane-paved tar can be used. The old rubber may vary depending on Desire to be dissolved first in the petroleum solvent in order to achieve a homogeneous stock solution, whereupon the stock solution and the asphalt material or petroleum tar can be co-heated to form the desired mass of asphalt achieve.

The asphalt masses produced according to the invention have good ductility at low temperatures, durability, resistance to oxidation and a low Temperature sensitivity. The asphalt masses are suitable excellent for use as elastomeric masses for the repair of plaster pavements.

Asphalt compositions with a penetration value between 40 and 300 (ASTM D-549) can be achieved by adding an appropriate amount of coal-made asphaltenes, solvent-refined coal, and wood. They are also suitable as binders in road construction. The hardness of the asphalt compositions according to the invention can be changed as desired by blowing air with or without the presence of a catalyst such as phosphorus pentoxide or zinc chloride. The preferred asphalt compounds have a Riag and Ball softening point between 65.6 and 58 ° C (150 and 185 ⁰ P) and an extensibility of more than

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100 cm at 25 ⁰ C (77 ⁰ P-ASTM D-113-44).

Improved masses for road pavements and road surfaces can be achieved that the homogeneous Pitch or asphalt mass is added as an additive to the known and more common asphalt binders for paving. The elasticity, durability and adhesion of an AC-IO Asphalt cement (ASTM D-3381), for example, can do this be improved that 5 to 50 wt .- ^ one with rubber mixed pitch or asphalt mass in this asphalt cement can be heated and made soluble

Other non-petroleum materials such as coal or wood; can be used in the manufacture of synthetic pitch and asphalt. It has been found within the scope of the invention that the fraction of the highly heat-resistant residue product resulting from the catalytic fluid cracking (PCC) is an excellent solvent for coal and the like, since this residue product is about 0.3% or more labile hydrogen, about 1.5 Contains% or more benzyl hydrogen (alpha), about $ 2 or more aromatic hydrogen, and about 4 % or less beta, gamma, or other hydrogens.

In this embodiment, a sludge is formed from waste rubber, coal and petroleum solvent. The petroleum solvent is, as described above, a thermally stable, oil refinery fraction boiling 232-593 ⁰ C (450 and HOO ⁰ P). The slurry thus formed is then heated to a temperature wipe "177 and 454 ⁰ C (350 and 850 ⁰ P) via a tent margin heated sufficient to the slurry in a

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to convert homogeneous mass with the desired pitch-like asphalt properties at temperatures below 93.3 ⁰ C (200 ⁰ P).

The ratio of old rubber to dissolved coal can be between 0.01 and 10 in this embodiment Parts by weight of old rubber per part by weight of coal, preferably between 0.05 and 5 parts by weight of old rubber per part by weight Coal fluctuate.

The petroleum solvent component of the sludge is preferably in an amount between 0.1 and 1 5o, preferably between 0.5 and 2o parts by weight of petroleum solvent per part by weight of that combined in the sludge Weight of old rubber and coal.

Do nominal analyzes for various examples of coals that are suitable for this embodiment are as follows:

highly volatile A

sulfur 1.33 % nitrogen 1.63 oxygen 7.79 carbon 80.88 hydrogen 5.33 ash 2.77

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Sub-bituminous

sulfur Brown coal sulfur 0.21 nitrogen nitrogen 0.88 oxygen oxygen 15.60 carbon carbon 65.53 hydrogen hydrogen 5.70 ash ash 3.99 0.53 0.74 32.04 54.38 5.42 5.78

If charcoal is present in the mixture to be dissolved, it can be advantageous to place the mixture under hydrogen heat and dissolve at a pressure between 7.03 at and 141 at (100 and 2000 psi).

It can also be used as an additive for the component or in place of part or all of the wood Carbon component can be added to the mixture. It can therefore produce a homogeneous pitch and / or asphalt mass that an additive with 5 "to 20% by weight of crushed Waste rubber, 10 to 30% by weight of crushed coal, 10 to 30% by weight of crushed wood (for example Bog oak) and 20 to 75 wt .- ^ petroleum solvents (for example syntower residues or main column residues) is heated and dissolved.

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When the slurry of petroleum solvent and other components has been heated for a sufficient period of time is a liquid, homogeneous mass. The homogeneous mass can continue to undergo a release process before cooling, such as filtering, centrifugation, settling are subjected to the liquid phase of the mass of any remaining Separate pesticide particles, ash or other insoluble materials that are suspended in the mass could be. This technique improves the pitch and asphalt compounds for the production of bitumen paints, coatings, Adhesives and other high-quality commercial products.

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Claims (12)

Claims 1. A method for producing a pitch-like Hasse, characterized in that a sludge of old rubber and a petroleum solvent with a thermally stable petroleum fraction with a boiling point between 232 and 593 ⁰ C (450 and HOO ⁰ F) is formed and the sludge at a Temperature between 177 and 454 ⁰ C (350 and 85 £ ° F) for a period of time sufficient to turn the sludge into a homogeneous mass with a soft, pitch-like con- et
(-20 and + 20O ⁰ F) to convert. resistance at temperatures between -28.9 and +93.3 ⁰ C 2. The method according to claim 1, characterized in that the sludge is heated for a period of time between 0.2 and 3 hours. 3. The method according to claim 1 or 2, characterized in that the petroleum solvent has a boiling point between 343 and 593 ⁰ C (650 and HOO ⁰ F). 4. The method according to any one of claims 1 to 3, characterized in that the petroleum solvent is a main column or syntower residue, a heavy return oil, a clarified sludge oil, a petroleum residue, a propandesasphalted one Tar or a coker gas oil. 5. The method according to any one of claims 1 to 4, characterized in that the petroleum solvent in an amount from 0.5 to 50 parts by weight of petroleum solvent per part by weight Old rubber: · β · sludge is present. 709835 / 079b ORIGINAL INSPECTED 6. The method according to claim 5, characterized in that daa petroleum solvent in an amount of 0.5 to 20 Parts by weight of petroleum reading agent per part by weight of waste rubber is present in the sludge. 7. The method according to any one of claims 1 to 6, characterized in that an asphalt material obtained from coal, Petroleum or wood is added to the homogeneous mass to produce a synthetic asphalt. 8. The method according to claim 7, characterized in that the weight ratio of old Kautsduk to asphalt material ranges from 0.1: 1 to 10: 1. 9. The method according to claim 7 or 8, characterized in that that the petroleum solvent in an amount of 0.5 to 50 parts by weight of petroleum solvent per part by weight of the combined weight of ariAlt rubber and asphalt mixture in the Sludge is present. 10. The method according to any one of claims 1 to 9, characterized characterized in that the sole is brought into the mud with the waste rubber. 11. The method according to claim 10, characterized in that the weight ratio of old rubber to coal in Sludge is between 0.01: 1 and 10: 1. 12. Use of a mass produced by the method of claims 1 to 11 for road construction, as a sealing material, Casing for pipelines, impregnating agents and inner linings for pipelines, and for the manufacture of Cardboard and insulating materials. 709835/0796 13 · Use one according to the method of claims 7 to 9 produced mass for the production of an asphalt binder, that from a mixture of road asphalt and from 5 to 50 percent by weight of the produced according to claims 7 to 9 Mass, based on the total weight. 70983b / 079ti