DE2300885C3 - Process for the manufacture of fiber tubes impregnated with non-oxidized petroleum pitch - Google Patents

Description

There are already impregnation and paint known, which in addition to a bituminous carrier Contain a large amount of aluminum pigment. In addition, US-PS 14 65 107 with a coating compound Paper coated from bituminous substances, in particular petroleum oil, and metal powders described.

The invention is based on the object of a process for the production of non-oxidized To create petroleum pitch impregnated fiber pipes in which very little aluminum pigment is used. This object is achieved by the invention

The invention thus relates to a process for the production of non-oxidized petroleum pitch impregnated fiber tubes, which is characterized in that one tubes made of fibrous material in a Impregnating compound containing buoyant aluminum pigment in an amount of 0.1 to 1.4 percent by weight dipped from molten non-oxidized petroleum pitch and then allowed to cool

The fiber pipes to be impregnated must be made in such a way that the impregnation compound Immersion can penetrate into them. Furthermore, the fiber tubes must be used for impregnation Temperature be stable. The impregnation compound should only have a low viscosity at these temperatures, so that it can penetrate sufficiently into the fiber tubes. At the same time, however, it has to Have sufficient hardness at room temperature.

In addition to the floating aluminum pigment, the impregnation compound preferably contains only small amounts Quantities of filterable suspended components, for example carbonaceous solids, dirt or mineral slag. If the masses contain too large a proportion of filterable suspended constituents, this indicates End product unsightly surface deposits or the impregnation is incomplete. the The acceptable amount of suspended constituents in the impregnating compound depends on the impregnating compound Fiber tubes, for example by their porosity and wall thickness, the particle size of the suspended Material and the viscosity of the impregnation compound. Test method for the determination of filterable components in impregnating compounds are known in the art

Any buoyant aluminum pigments are suitable for the purposes of the invention Classification and grading of aluminum powders and pastes depends on the individual manufacturer However, one of the most common classifications is the one summarized in Table I. the American Society for Testing Materials.

Table I.

ASTM classification 962-66

(max.overflow (percent) a 44μ sieve)

Classes
A. fine

B. medium

C coarse

1. Floatable aluminum pigment powder

2. Floatable aluminum pigment paste

3. Non-floating aluminum pigment powder

4. Non-floating aluminum pigment paste

0.1 1.5 20th υ, ι 1.0 15th 1.5 6.0 20th 0.1 1.0 11th

The amount of aluminum pigment added to the impregnation compound as a powder or paste depends on various factors Circumstances. On the one hand, aluminum pigments are quite expensive, so that only the Usable coating of the fiber tubes necessary amount is incorporated. The minimum quantity required depends on the desired properties of the object.

The impregnation takes place in the usual way, for example by soaking in an open container a certain period of time or by impregnation under pressure or vacuum or combined pressure-vacuum application. The last-mentioned process is preferably used.

For the impregnation of fiber pipes according to the invention with the suspended aluminum pigment containing impregnation compounds are used in the usual way made of fibrous pipes Material. Such tubes are created, for example, when winding up wet webs of cellulose pulp a spindle. As soon as the desired wall thickness has been reached, the pipes are removed before or after acceptance dried off the spindle. Processes for making dried paper tubes are for example from the US-PS 18 03 409,18 54 230 and 18 60 674 known

A suitable pitch for the production of the fiber pipes impregnated with bituminous masses is non-oxidized petroleum pitch.
Unoxidized petroleum pitch can also be referred to as unmodified thermally generated petroleum pitch. This pitch remains solid up to temperatures just below its melting point. For the production of non-oxidized petroleum pitch, it is preferred to use clarified sump oil or cracked oil, which has been largely freed from paraffins by catalytic cyclization. If this is not possible through catalytic cracking alone, the paraffins can be mixed with furfural from the sump oil or from circulating oil

23 OO

extract. The raw material obtained consists in the production of non-oxidized petroleum pitch is for each case from a highly aromatic oil with an example in U.S. Patents 2,768,119 and 3,140,248

snowing up. In Table II are the properties of

IgQg [Jl r <* Ji * »--— ■ _ .. ■» ... ... vw-.H · wKiHktuviivii v ^ i Hill tin

Boiling point of about 370 to 455 ° C. This oil can withstand higher temperatures and pressures for as long as possible. λ cracked until a petroleum pitch with a softening point of about 65 to 100 ° C is obtained. the

four non-oxidized Pertroleumpechen (A, B, C and D) 5 combined.

Table II

test Test standard Bad luck A Bad luck B Bad luck C Bad luck D Softening point, ⁰ C (ring bed process) ASTM D-2398 78.3 78.9 75.8 74.4 Density, g / cm * Mettler 1.192 1.205 1.160 1.178 Carbon content, weight percent ASTM D-2416 37.8 43.8 39.6 36.9 Flash point COC, ⁰ C ASTM D-92 282 257 285 279 Softening depth J 00/5/77 ASTM D-5 0 0 0 0 Softening depth 200/60/115 ASTM D-5 128 47 208 Softening depth 50/60/15 ASTM D-5 40 37 68 Sulfur content, percent by weight ASTM D-1552 2.73 1.47 2.01 0.95 Ingredients insoluble in benzene, percent by weight ASTM D-2317 0.80 11.7 1.9 2.3 Ingredients insoluble in chinoun, ASTM D-2318 0.11 ') Weight percent Viscosity cP (# 2 spindle, 30 rpm) 350 Brookfield 40 70 45 32 325 Brookfield 60 110 82.5 65 300 Brookfield 140 230 165 135

I) Filtration impossible because the solids content is too high.

For the production of waterproof and weatherproof fiber pipes, the use of floating pipes is recommended Aluminum in combination with non-oxidized petroleum pitch is required when using a fiber tube wants to produce with a smooth, metal-colored or aluminized outer and inner surface.

The amount of the powdery or pasty aluminum pigment used in the pitch mass depends on various circumstances. The minimum quantity is to be chosen so that the end product is the desired The maximum amount is determined by the economy of the Procedure, whereby at the same time it should be noted that if the content of filterable aluminum pigment in the pitch mass is too high, an only incomplete one Impregnation takes place The impregnation compounds made of pitch and aluminum contain 0.1 to 1.4 percent, preferably 03 to 0.7 percent aluminum pigment. This aluminum concentration only relates on aluminum metal and does not include additional solvents or stabilizers.

Should the pitch-impregnated pipes not only have improved moisture and weather resistance have metalized or aluminized outer and inner surfaces, the best results are achieved with the combined use of a buoyant aluminum pigment and a non-oxidized one (thermal) petroleum pitches. The term "buoyant" refers to the fact that certain metal pigments occur in the form of thin leaflets. If you mix such pigments with one Binder and coated an object rr.it of this paint, the thin flakes float up and collect on the surface of the Paint films, overlapping each other. For the production of mirror-forming aluminum pigment aluminum powder is treated with a so-called leafing agent, for example stearic acid. Through this the risk of explosion is reduced at the same time. Build-up floating aluminum pigment can go through Milling of aluminum in a ball mill in the presence of gasoline hydrocarbon or the like Solvents are produced. An aluminum paste is obtained when the mixture is filtered. A For example, commercially available floatable aluminum pigment in paste form has those in Table III called composition.

Table III at least 68.0% Non-volatile components max. 14.0% Sieve overflow (44 μ) max. 0.1% Moisture content Petrol coals solvent Hydrogens 0.67 liters / kg Bulk volume 5.68 kg Weight per 3.79 liters Particle size distribution 85% 0.5-44 µ 7% 44-150 µ

Non-buoyant aluminum powder in combination with non-oxidized petroleum pitch also results metal-colored or aluminized tubes. This is probably due to the fact that the suppression of the Mirror formation added stabilizer when the aluminum pigment is heated to the temperature of the melted petroleum pitch is decomposed and so the aluminum practically as a floating pigment works. So although buoyant aluminum powder is preferred for the production of metal-colored or aluminized pipes are used, non-floating aluminum powders are also suitable for this purpose, as they act as floatable pigments at the impregnation temperature.

23 OO

When manufacturing pitch-impregnated fiber pipes with the aid of aluminum pigment and petroleum pitch, the two components can be mixed in various ways to form an impregnation compound.If the aluminum pigment is in the form of a paste in a liquid carrier, this can be added manually to the molten pitch and mixed with it by stirring or circulation mixed with this. The temperature of the aluminum powder / pitch mixture during the impregnation is preferably in the range from about 135 to 190 ^° C. The temperature naturally depends on the properties of the pitch in question.

The impregnation of dry paper tubes is carried out in any way; It only has to be ensured that the pitch penetrates into the pores and gaps in the paper tubes.A preferred method consists in placing the paper tubes in a pressure vessel and evacuating it for a few minutes.Then the molten impregnating compound is pumped into the pressure vessel until the tubes are covered are. By circulating the molten mixture for a few minutes, the pitch and aluminum are evenly distributed. The pressure in the boiler is then increased to atmospheric pressure and the pitch penetrates the pores of the paper tubes. The molten aluminum powder-pitch mixture remaining in the kettle is drawn off; the tubes are also removed and allowed to cool.

It has not yet been clarified exactly on which processes the effect that can be achieved according to the invention is achieved

IO u ht 7, mächst occurs naturally some filter - "^ .Äderdas suspended aluminum powder ^WI Vechschicht on the surface of paper tubes e Using another pitch ridiertes petroleum pitch and capable aluminum powder, the aluminum powder .st in Oberflächenierten pipe less obvious TumiSSen even not detectable. Usually the black pipe surface has a metamical sheen. When using S Ptlumpech and floating

See at the

■ ' and surrender

Coal pitch and 85 percent ni

Vsi & MKcrs:

? % cm and a wall thickness of 635 mm. The results obtained when testing the specimen are summarized below:

Creep Deformation ¹ ) 2 £ 4mm (Average) 2.13mm Water absorption ² ) 1.04% (average) 0.75 and 60% max. 2% Axial dry strength *), kg / m 1190 (average) 1370 1190 Flattening ⁴ ) 0.80% (average) 0.69 and 0.65 max. 3%

') Creep deformation (mm) per 5.08 cm of the pipe section after 23 hours at 7031 at and 20 ° C;

² ) percent weight gain after immersion in water for 48 hours at 21.1 ° C and atmospheric pressure;

Ά breaking load (kg / m);

⁴ ) Percentage decrease in diameter at 48.9 ° C and a load of 119 kg / m.

It can be seen from the table that the aluminum-aluminized pipe, which is different from the impregnating compound, has properties that are superior to powder concentrations. The pipe diameter The one produced with the help of the usual impregnation compound is again 11.27 cm and the wall thickness th pipe owns. 635 mm.

Further pieces of fiber pipe are made with the help of 5 ° The following results are achieved: Petroleum pitch (sample D from Table II) impregnated,

Sample 'pipe impregnation compound

_Λ 0% Al

100% petroleum pech) B 0.17% Al *)

C 034% A $

D 0.68% ΑΠ

18.29

17.78 17.27 18.29 1.68-1.94

1.48-1.83 1.58-1.57 ⁷ ) 1.17-1.26

1250-1190

1075 1135-1040

1 ^ 1-3.87

1.96-2.10 2.04-2.18 1.06-1.37

ι) Creep formation (mm) per 5.08 cm per length after 1 hour at 70.31 at and 20 ° C;

² ) percentage weight increase after immersion in water at 21.1 ° C. and atmospheric pressure for 48 hours;

³ ) Breaking load (kg / m);

⁴⁾ percentage decrease of the diameter of $ 48 ^O C and a load of 119 kg / m;

5) non-oxidized (thermal) petroleum pitch in all experiments; «) Percent aluminum in the total mixture;

η this deviation is based on an experimental error.

23 OO 885

Sections of pipes A, B and C are tested for 629 hours in a standard weatherometer (corresponding to 18 months of outdoor weathering). The following results are achieved:

Impregnation compound

Look

0% aluminum,
100% petroleum pitch
0.17% aluminum

034% aluminum

dull, dusty brown surface

slightly aluminum-colored, but still matt fiber surface

shiny aluminum coating, no dusting

In a further test, fiber pipe samples are produced with the help of the following impregnation compounds:

1. 20 percent coal pitch and 80 percent non-oxidized petroleum pitch,

2. 100 percent unoxidized petroleum pitch and

3. 1 percent aluminum and 99 percent unoxidized petroleum pitch having a softening point of 76.7 ⁰ C.

The following test results are obtained with the help of these test specimens:

20% Coal pitch 100% petroleum pitch 1% aluminum (NO) ¹ ) ASTM D-1861- 80% Petroleum pitch (NO) ¹ ) 99% Petroleum pitch default (NO) ') Through Area cut

Wet creep deformation ² ) 14.22 9.64 7.62-11.68 9.52 - Water absorption ') 1.13% 1.26% 0.78-1.02% 0.90% max. 2% Water absorption 3.37% 3.85% 2.0-3.8% 2.82% - (200 hours) *) Axial dry strength 1700 1730 1640-1880 ⁷ ) 1740 ⁷ ): at least 1250 kg / m ^s ). Flat ⁶ ) 1.10 1.47 0.78-1.62% 1.17% max. 3%

') NO means unoxidized petroleum pitch;

² ) the dry sample is immersed in water and exposed to a fiber tension of 7031 atm for 336 hours (2 weeks);

³ ) percentage weight gain after immersion in water at 21.1 ° C. and atmospheric pressure for 48 hours; ⁴ I percent weight increase after immersion in water for 200 hours at 21.1 ° C. and atmospheric pressure; ⁵ J breaking load (kg / m);

^ percentage decrease in diameter at 48.9 ° C "and a load of 119 kg / m;

⁷ ) In this test, dry fiber pipes of inferior quality were used; the reduced axial dry strength is due to this fact.

In another test, a pipe that was impregnated with an impregnation compound made from 20 percent hard coal pitch, 1 percent aluminum and the rest of non-oxidized petroleum pitch was impregnated, after 5 days of immersion in water a water absorption of only 0.73 percent. In comparison, lies the water absorption of one with only 20 percent coal pitch and 80 percent petroleum pitch impregnated pipe section after 5 days at about 1.5 percent

In addition, the fiber tubes produced with the aid of the impregnation compositions of the invention have the following Advantageous properties: The aluminized pipe sections are easy to handle, especially mil bare hand and thin gloves. They do not heat up when exposed to intense solar radiation as usual pitch-impregnated pipes to high temperatures. In addition, the aluminized tubes can be removed Cuts are easier to load because they slide together more easily than conventional pitch-impregnated pipes.

709 647 /

Claims (2)

23 OO claims: 1. a process for the manufacture of fiber tubes impregnated with non-oxidized petroleum pitch, characterized in that one tubes made of fibrous material in a buoyant Impregnating compound containing aluminum pigment in an amount of 0.1 to 1.4 percent by weight melted non-oxidized petroleum pitch and then allowed to cool 2. The method according to claim 1, characterized in that the impregnation compound 03 to 0.7 Contains percent by weight of buoyant aluminum pigment