DE1966045A1 - Resinous pitch compositions - Google Patents

Abstract

The pitch is prepared by cracking a petrol hydrocarbon at 700 - 2500 degrees C with a contact time of 0.001 - 2 seconds to produce a tarry material which is heated to between 250 and 450 degrees C to eliminate volatiles. The final material has an atomic H/C ratio between 0.4 and 0.65, a softening point between 70 and 400 degrees C and 40 - 90% insoluble in benzene. It is powdered to a mesh size between 2 and 80. Aresin is produced by adding 7 - 200 parts of an aromatic hydrocarbon of density 1.0 to 1.3, a H/C ratio 0.5 to 1.0 and a boiling range between 250 and 450 degrees C. To the above may be added a solid material, specifically 50 - 2500 parts of an aggregate, the whole being allowed to harden ot a predetermined shape, pref. at 10 - 150 degrees C.

Description

Methods of Making Pitch Compositions The invention relates to relates generally to petroleum hydrocarbon products and particularly to pitch. The pitches according to the invention contain aromatic rings or aromatic rings as constituents and aliphatic rings.

Pitch-like substances are generally used for protective purposes, for example for thermal insulation, sealing and heat or heat shielding. For such purposes, an asphalt called gilsonite is known, which is used by the American Gilsonite Company.

Although gilsonite is an extremely useful material its quality is not necessarily always constant, since it is is a natural bituminous substance. Furthermore, a natural product is not available In any close available at any time, so that if necessary the demand cannot be satisfied. This results in the general objective of the invention, namely to create a synthetic material that has a consistent quality and that can be produced in large quantities without too much effort.

Numerous attempts have been made so far, from the Petroleum refining produced asphalt fractions materials, their structure and properties are similar to those of gilsonite. But so far it is ndch failed to produce a powdery material in an economical way, its Properties are comparable to those of gilsonite.

Perner is known to use bituminous materials for construction purposes, For this purpose, these substances are generally at or above their softening temperature heated or blended with suitable light oils. A liquid is then obtained or flowing material that can be easily processed. When intersecting, reduces the viscosity of the asphalt or pitch-like material. This is on the dissolution of the asphalt or pitch-like material in the added light oils traced back.

This will improve the usability and preservation properties of the bituminous material improved over long periods of time.

Most of the added light oil evaporates after the bituminous material is applied.

In principle, the object of the invention is to provide synthetic To create pitch compositions or mixtures of pitches that preserve the natural asphalt are also necessary. In particular, powdery synthetic pitch compositions are intended are created, their usability and their properties at least the same or better than those of natural bituminous substances. Furthermore should the pulverulent pitch used for this cause the adding and mixing Slurried pitch mixture created by additives and aromatic oils into solid ones Solidified molded objects.

The invention relates to a method for producing pitch masses, which is characterized in that a tar substance obtained by cracking a Petroleum hydrocarbons at a temperature of 70,000 to 25,000C and a contact or Contact time of 2 to 0.001 seconds was obtained for Removal of light oil including volatile components from it under atmospheric pressure heat-treated or reduced pressure at a temperature of 2500C to 4500C, the pitch substance obtained as the end product having a hydrogen / carbon atomic ratio from 0.4 to 0.65, a softening point of 700C to 4000C, one insoluble in benzene Proportion of 40 to 90 percent by weight, a specific weight of 1.2 to 1.5 and a grindability to a particle size of 4.699 mm to 0.065 mm (mesh 4 to mesh 250) and that this end product is ground in order to convert it into powder form.

Further details of the invention are based on preferred Embodiments explained.

The pitch mixtures produced according to the invention differ in terms of their chemical structure completely from natural asphalt, which a large number of side chains and linking chains with paraffinic carbon as shown in X-rays. The pitch mixtures according to the invention consist mainly of aromatic rings or aromatic and aliphatic rings Rings with few side chains and binding chains that are also on paraffinic Based on carbon.

The pitch mixtures or pitch compositions according to the invention, compared to the well-known natural asphalts and other bituminous substances Equivalent or better characteristics; 6en, according to the invention be prepared that during a first reaction or process step including a petroleum hydrocarbon Crude oil at a temperature thermally decomposed from 700 OC to 2500 OC for a period of 0.001 to 2 seconds is that the resulting tarry substance during a second reaction or process step at a temperature of 250 0 to 450 0 for removal is heat-treated by light oil and that the residue formed is pitch will be produced.

If after the first process step a normal hydrogenation undertakes in which some of the aromatic rings are converted into aliphatic rings is, and then carries out the second process step, is also obtained a pitch that has extremely desirable properties.

During the second process step, air can be used continuously blow into the treated fabric.

In the first reaction step, the petroleum hydrocarbon is a consequence decomposed to the high temperature. A part of the hydrocarbon is converted into one gaseous substance containing olefin, converted and at the same time part of it polycondensed, this part in a polycondensation product from predominantly condensed (fused) aromatic rings is implemented. There will be those Substances such as nitrogen and oxygen, which tend to have polar structures or To create structures, almost completely gassed and removed.

For this reason, a decomposition temperature of over 900 oC preferred. However, at a decomposition temperature of less than 900 oC one can also produce a product that resembles that at a decomposition temperature of over 900 oC is equivalent to the product produced by applying a heat treatment, in which decomposition and dealcoholization occurs.

The purpose and importance of the second reaction step mentioned above is that for the production of a pitch contained in the tarry substance oily substances that arise in the first reaction step are removed. This second step is preferably at atmospheric pressure or at reduced pressure Pressure and within a temperature range of 250 C to 450 oC. Below a temperature of 250 0a remains a part of the light oil, whereby the properties the pitch composition or pitch mixture can be adversely affected.

At a temperature higher than 450 ° C, the properties deteriorate bad luck too, because coking occurs.

In the case of the one carried out before the second reaction or process step Hydrogenation converts some of the aromatic rings into aliphatic rings, whereby the softening point of the product is reduced. This can after Pitch produced according to the invention can be processed more easily and is obtained in particular for the powdered or powdered pitch a larger area of application. It is very difficult to determine the structure of the fabric made according to the invention describe. However, it is a group of compounds that one at which receives condensation from many aromatic rings.

The tarry substance that can be obtained after the procedure described a high temperature of more than 700 0 and the preparation of the pitch composition is used today is a by-product that is found in large quantities, for example in the petrochemical industry, which produces olefins, and in the gas producing industry occurs when crude oils and heavy oils are decomposed at high temperatures. Included this substance is generally considered to be a waste product.

For the hydrogenation carried out according to the invention and for the as No special heat treatment is required for the second process step Apparatus or facilities.

It is also advantageous that the softening point of the product can be changed without making the process considerably more complicated and the advantageous properties of the powdery pitch are adversely affected will. Since the starting material of the pitch produced according to the invention in large If quantities are present and practically occurs as a waste product, one can get the bad luck produce according to the invention much cheaper than the Naturaaphalte used today.

The powdery one produced by the process according to the invention Pitch is particularly suitable as an insulating material. For this purpose the material is intended have the following properties: Color: brown to brown-black Weight: 1.200 to 1.500 softening point: 70 0 to 400 oO Component insoluble in benzene: 40 to 90 percent by weight (measured according to Japanese industrial standards JIS-K 2421) Grindability: Grain size 4.699 to 0.065 mm (mesh size 4 to 250) hydrogen / carbon atomic ratio (H / C ratio): 0.4 to 0.65 If you use the powdered pitch according to the invention the genaten properties used as protection and insulating material, then it delivers far better results than the conventionally used natural asphalt, in particular in terms of water repellency, water resistance and thermal insulation.

If you use the pitch according to the invention as a coating material on metal surfaces used, then it sticks to the metal surfaces much better than the conventional ones Fabrics.

The fabric of the invention has been used for protection and thermal insulation proved to be extremely useful by various types of piping, for example in pipelines for cold water, hot water and steam as well as for underground laid pipes.

Under the term "powder" or "powdery" or "powdery" Material1: a powder material is to be understood here, the grains of which are replaced by a Sieve with a clear mesh size of 4.699 mm (mesh size 4).

Depending on the nature of the intended use, this can be done according to the invention Pitch produced, for example, as a protective material without any additional materials use. But you can also add different materials, for example bituminous Materials such as asphalt, coal tar pitch and natural asphalt, as well as inorganic ones Substances such as clay, silica and pearlite.

That is in the solid state. pitch according to the invention, the is processed only after a so-called. Slurry process, has various advantages. It is easy to work with and hardens easily. Furthermore, it is light, water-resistant, chemically resistant, corrosion resistant, extremely strong and has many desirable ones Properties. For this reason, the pitch composition of the present invention has, for example as a building material a very large area of application compared to conventional Cement mortar and concrete. The pitch composition according to the invention can be used, for example as building material for foundations, pillars, walls, ceilings, floors and fences, as road building material, Drainage pipes, bridge girders, foundation pillars, coastal protection blocks, cladding, Dams to hold back earth, boundary posts, flooring, roads and high voltage amasts use.

For more details on the type and intended use To give the material according to the invention are preferred embodiments below described, which, however, serve only for explanation and not the invention should restrict.

Example 1 Naphtha is at a reaction temperature of 12000C and decomposed after a contact time of 0.03 seconds.

This results in a tar-like substance. The tarry substance will divided into three samples. The samples are distilled dry, to remove further light oil and volatile components .. Then be the samples ground using the powdered pitch composition according to the invention receives.

Sample 1: dry distillation at 450 ° C. Sample 2: dry distillation at 350 ° C sample 3: hydrogenation at 250 oO for 12 hours with an initial Hydrogen pressure of 100 kg / cm2 in the presence of a hydrogenation catalyst, which by Deposition of 15% nickel on diatomaceous earth is formed. Then takes place a dry distillation at 350 ° C. The samples prepared in the above manner have the following properties: In benzene sample H / C- spec. insoluble relationship Weight part 1 0.51 1.38 70 2 0.53 1.35 65 3 0.65 1.25 50 These samples are in given a tube with a diameter of 3 cm. The in the pipe has Material a length or thickness of 5 cm. Furthermore, 1 cm below the surface of the A blood electrode is arranged in the sample located in the tube. The ones arranged in the tubes Samples are exposed to water under pressure. The pressure is now measured where water seeps through the sample. This is done by a connected to the electrode Measuring device displayed.

These Wessungen can be used as a measure of the water-repellent property of the samples can be used.

In Table 1 below are the water-repellent properties of the samples according to the invention compared to two conventional, Specified commercially available asphaltenes. Here is the particle size for the Samples are chosen so that all particles pass through a sieve with a clear mesh size of 0.147 mm (100 mesh), but not through a sieve with a clear mesh size from 0.074 mm (200 mesh).

Table 1 Sample melting point water (° C) repulsive characteristic (kg / cm2) 1 230-250 1.0 2,160-170 0.95 3 130-140 0.8 Natural asphalt (A) 60 - 165 0.5 Natural asphalt (B) 135 - 140 0.3 As can be seen from the table, the water-repellent properties of the pitch compositions according to the invention are significantly better than those of the known natural asphalts.

Furthermore, long-term tests lead to the result that at one pressure of 0.5 kg / cm2 the natural asphalt (A) lets water through after just one hour, whereas under the same pressure for the pitch composition samples of the present invention 1, 2 and 3 no water seeping through even after a week is. DXes illustrates the considerable progress of the material according to the invention in terms of water repellency and water resistance.

Example 2 A concrete bracket is placed outdoors in the ground and attached a 1-inch pipe to it. Next, the pipe with the sample 1 surrounded by example 1 with a thickness of 10 cm. By pounding the material condensed.

The sample 1 is then covered with a 30 cm thick layer of soil and Covered with sand, which is also compacted. If you get the pipe after three months exposed, then it is completely unchanged and shows no rust or corrosion damage on.

If instead of sample 1 under the same conditions described above If you use the natural asphalt (A), the pipe will be attacked by rust after three months.

Perner was after stomping on part of the invention Coating material measured the thermal conductivity and density. Here one obtains the following results: thermal conductivity: 0.055 kcal / h / m2 / OC / m density: 0.68 g / cm3 Example 3 Naphtha is at 1250 O0 during a contact time of 0.002 Seconds to form pitch. After removing parts with a The pitch is ground with a boiling point lower than 450 ° C. This pitch has an H / C ratio of 0.53, a component insoluble in benzene of 65%, a softening point between 230 OL: and 240 ° 0 and a specific gravity of 1.35. Those particles of the ground pitch, which is passed through a sieve with a mesh size of 0.147 mm (100 mesh) but not through a sieve with a mesh size of 0.064 mm (mesh 250) drops are collected.

These collected pitch particles become an aromatic hydrocarbon oil added, which is a fraction (H / C ratio 0.85, specific weight 1.15, aromaticity according to NMR 75%) from 250 ° C. to 450 ° C., which is obtained by distillation of the tarry substance obtained under the above decomposition conditions will. The combined substances are mixed and left at room temperature calmly. Samples with different mixing ratios are produced. The hardening of the individual samples is dependent on the depth of penetration or Penetration measured according to the Japanese industry standard JIS-X 2207. The results are shown in Table 2.

Table 2 Mixing ratio penetration (according to JIS - K2207) Bad luck- Aromatic- Immediately composition after after after after Sample (weight water niches 1 day 2 days 3 days parts) fabric oil (Weight parts) 1 100 20 35 20 13 10 more than 2 100 50 45 35 25 more than 3 100 100 75 60 50 200 4 100 2pO more than 115 98 70 200 Example 4 Sample 1 of Example 3 is heated and cured. It takes one hour at 80 ° C to achieve a penetration of less than 20. At 120 ° C you need five minutes less. For Sample 3, the respective times are 7 to 8 hours at 80 ° C and 1 hour or less at 120 ° C in order to reduce the penetration to less than 20.

Example 5 The pitch produced according to Example 3 is divided into three groups with a grain size of 4.699 mm to 0.246 mm (mesh 4 to mesh 60), of 0.246 mm to 0.147 mm (mesh 60 to mesh 100) and from 0.147 mm to 0.065 mm (mesh 100 to mesh 250). In each case 100 parts by weight of these divided according to grain size Groups are 20 parts by weight of the aromatic hydro described in Example 3 oil added.

The combined substances are mixed and kept at room temperature hardened.

The pitch with the small particle size hardens much faster than the pitch with the large particle size, because the first pall has a larger surface is available. The result is shown in Table 3.

Table 3 Penetration (according to JIS K2207) Particle Size Immediately After After (after "mesh") after the 1 day 2 days 4 - 60 7200 38 -25 60 - 100 44 27 14 100 - 250 35 20 13 Example 6 The kerosene fraction of petroleum (paraffin oil or lamp oil) is decomposed at 1350 0a and a contact or touch time of 0.001 seconds to produce a pitch-like substance. The lighter, more volatile constituents with a boiling point below 450 cc are removed from this substance.

The pitch composition produced in this way has an H / G ratio of 0.51, a component insoluble in benzene of 7o ', one Softening point of 250 ° C and a specific weight of 1.40. This bad luck is ground su powder.

80 parts of this powder, with a particle size of less than 0.246 (mesh 60) are mixed with 100 parts of sand with a particle size of 0.833 mm to 0.495 mm (mesh 20 to mesh 32) mixed. The sand serves as an additional material or Aggregate.

This mixture is 20 parts of the aromatic described in Example 3 Hydrocarbon oil mixed in to form a slurried or pasty mass obtain. The slurry is hand mixed and allowed to stand for two days. This gives a material that is particularly suitable for building purposes and its specific weight 1.6 and its compressive strength is 240 kg / cm2.

This material produced according to the invention has a water adsorbability of almost 0% in contrast to cement or concrete, whose adsorptive capacity is about 10%. This material is therefore particularly suitable for mining and civil engineering.

Example 7 Naphtha becomes at 1300 0 and a contact or touch time decomposed by 0.002 seconds. This creates a pitch composition with an H / C ratio of 0.52 and a component insoluble in benzene of 70%. This pitch composition is ground to a powder with an average particle size of 0.175 mm (mesh 80). The pitch is mixed with sand in a mixer.

An aromatic hydrocarbon oil is added to this mixture, which is obtained after the same decomposition as given above and which is a H / C ratio of 0ç85, a specific gravity of 1.10 and one measured by NMR Has an aromaticity of 70%. The two materials are thoroughly mixed up, The mixture is in a block with Dimensions of 10 x 10 x Poured 3.0 cm and left for two days. After that, the compressive strength of the block produced in this way. The results are for different ones Mixing ratios shown in Table 4.

Table 4 Aggre- Aromatic pressure strengthening- at bad luck hydrocarbon specificity 2 Sand) material oil weight (kg / cm2) (Parts by weight) 100 80 20 1.52 245 200 80 20 1.56 300. 400 80 20 1.57 - 120 600 80 20. 1.59 70 Since the compressive strength of conventional concrete is approximately 350 kg / cm 2 and the specific weight is 2.0, the materials produced according to the invention are quite on a par with conventional concrete.

Example 8 A slurried fabric, which by niches with the same Materials is prepared in the same manner as indicated in Example 7 is cast into block samples under a pressure of 100 kgXcm2. The for this The values measured for block samples are compiled in Table 5 below.

Table 5 Aggre- Aromatic pressure strengthening- gat pitch hydrocarbons specific speed (Sand) oil weight (kg / cm2) (Parts by weight) 100 80 20 1.65 280 200 80 20 1.75 340 400 80 20 1.77 150 The measurement results show that the material according to the invention is absolutely comparable with concrete, which has a compressive strength of 350 kg / cm2. The compressive strength of the material according to the invention can be increased by applying pressure.

Example 9 Perlite (Type 1 from Ube Kozan) is used with the pitch from Example 7 mixed. The aromatic oil described in Example 7 is also mixed in. The mixture is poured into blocks with dimensions of 10 x 10 x 30 cm and for left for three days. The compressive strength then measured is compiled in Table 6.

Table ó Perlite pitch aroma spec. Pressure thermal conductivity table weight strength 01 (kg / cm2) (kcal / h / m2 / ° C / m) (Parts by weight) 100 70 30 0.9 130 0.15 200 70 30 0.8 75 0.098 400 70 30 0.7 50 0.066 A heat protection wall for a cold room was built from the blocks, which were cast by hand. Excellent results were obtained.

Example 10 Another great advantage of the pitch compositions according to the invention, their property is to repel water and to withstand water. These properties were matched with the corresponding properties of Portland cement compared.

The results are shown in Table 7. That in this example The pitch and aromatic oil used corresponds to the substances of Example 7.

Table 7 Sample sand perlite pitch aromatic cement water absorption great Ö1 ability (Parts by weight) (%) 1 100 - 80 20 - - 0 2 200 - 80 20 - - 0.5 3 - 100 80 20 - - 1.1 4 160 - - - 80 80 12.0 Samples 1 to 3 are pitch-containing materials according to the invention. Sample 4 is a comparative cement sample.

The absorption or absorption capacity of the manufactured according to the invention Pitch composition is much less than that of conventional cement mortar. As a waterproof foundation for underground pipelines is the invention Material excellently suitable.

Claims (3)

Claims 1. Process for the production of pitch masses that can be used It is noted that a tar substance is produced by cracking an oil hydrocarbon at a temperature of 7000G to 2500QC and a contact or touch time from 2 to 0.001 seconds for light oil removal inclusive volatile components from it under atmospheric pressure or reduced pressure heat-treated at a temperature of 2500C to 4500C, the end product being obtained Pitch substance has a hydrogen / carbon atomic ratio of 0.4 to 0.65, a Softening point from 7000 to 4000C, a portion insoluble in benzene from 40 to 90 percent by weight, a specific gravity of 1.2 to 1.5 and a grindability has a particle size of 4.699 mm to 0.065 mm (mesh 4 to mesh 250), and that one grinds this final product to convert it into powder form. 2. The method according to claim 1, characterized in that the by the substance obtained from cracking is subjected to hydrogenation before the heat treatment will. 3. The method of claim 1, d a d u r c h g e k e n n z e i c h n e t that air in the material obtained by the cracking during the heat treatment is blown.