DE1247522B - Process for the production of an impregnating agent for porous pipes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Clog

German class: 23 b-2/01

Number: 1247522

File number: St 19722IV d / 23 b

Filing date: September 17, 1962

Opened on: August 17, 1967

The invention relates to a method for producing an impregnating agent for porous pipes.

Tubular parts have been used for underground installation purposes for many years, e.g. B. as protective covers for telephone lines and electrical cables and as conduits for drainage, Sewage and other liquids.

To withstand the many unfavorable influences that occur during underground installation the tubular parts must have a number of exceptionally good properties, like impermeability,. high breaking strength and resistance to temperature influences, Corrosion and friction. Because the underground installations more or less in the long run are planned, the tubular parts should retain their initial properties over a long period of time keep.

It has already been proposed in the literature to use derivatives of coal tar and petroleum for impregnating porous pipes; as far as is known, however, no petroleum product has achieved significant economic success. Recent market research has shown that more than 90% of bitumen-treated conduit made from fiber in the United States has been impregnated with a derivative of coal tar. Part of the unfavorable assessment that petroleum products have received in this area may have been that the lines impregnated with these products did not conform to the standards laid down by the National Bureau of Standards in Commercial Standard Publication (CS-116-54) Testing correspond.

The inventive method for producing an impregnating agent for porous pipes is thereby characterized in that from a crude oil fraction boiling above 315 ° C the aromatics in itself extracted in a known manner and then oxidized by blowing with air. Preferably be the aromatics separated by treatment with a solvent, being particularly preferred Solvent furfurol is used. Air blowing is preferably carried out at room temperature.

The impregnating agents produced by the process according to the invention are uncoked with solvents extracted, oxygenated • condensation products of a distilled and clarified circulating oil. At the coking temperatures, the proportion of insoluble or insoluble in quinoline increases carbonaceous substances, what the impregnation

Method of manufacture
an impregnating agent for porous pipes ■

Applicant:

The Standard Oil Company,
Cleveland, Ohio (V. St. A.)

Representative:

Dr.-Ing. Dr. jur. F. Redies,
Dr. rer. nat. Β. Redies and Dr. rer. nat. D. Turk,
Patent attorneys,

Düsseldorf-Benrath, Erich-Ollenhauer-Str. 7th

Named as inventor:
John Carl Wisniewski, Parma, Ohio;
Thomas Harry Madden, Euclid, Ohio (V. St. A.)

Claimed priority:

V. St. v. America September 18, 1961
(138 992)

Λ

tion adversely affected. Accordingly, such temperatures should be used during the preparation of the impregnating agent be avoided. Extraction with solvents causes a concentration of aromatic Proportions required for the manufacture of a product that is highly resistant to kerosene are desirable. Extraction with solvents removes the non-resinous and the non-condensable Components. The proportion of aromatic substances is further increased by distillation non-resinous components are removed and the end products have an increased flash point. the Oxygen treatment of the molten material causes condensation - the aromatic parts, which effectively increases the molar weight of the material. The resulting The product is soluble in quinoline and practically insoluble in petroleum ether (bp = 30 ° C). The flash point after the distillation is at least 255 ° C.

The impregnating agent made from petroleum is a distilled, highly aromatic, chmoline-soluble, above about 315 ° C and preferably in the range of 370 to 420 ° C or approximately at 395 ° C, which is mixed with oxygen,

z. B. by blowing in Luits, up to a ring and ball softening point in the range of 65 to '120 ° C and preferably 75 to 80 ° C treated

709 637/603

has been. A particularly suitable, highly aromatic fraction is the Sdhwerölendfraktion, i. H. the second 50 percent by volume of the clarified circulating oil. For the purposes of the invention, the term »Clarified circulating oil (also known as» decanted «circulating oil) to describe the residue material obtained from the fractional distillation of the product from a catalytic cracking process used.

After the crude oil is initially separated by simple distillation, the Fraction that has a boiling range of from about 265 to 315 ° C up to about 535 to 595 ° C, one subjected to catalytic cracking processes. The cracked product is then in a column at the top fraction removed, one or more intermediate fractions and the column tray fractions (Residues) fractionated. Regardless of the type of catalyst used in the If cracking apparatus is used, considerable amounts of the powdered catalyst are removed from the Cracking apparatus is entrained in the fractionation part and collect in the aforementioned soil fractions at. These are separated from the catalyst by clarification processes known per se Cracking apparatus returned and cracked again. Because of this type of treatment, the The terms "circulating oil" and "clarified circulating oil" are used.

More recently, new uses for the paraffinic fractions of "clarified circulating oils" have been found. These new uses have brought the extractive treatment of "clarified circulating oils" to the fore, by means of which (1) the essentially aromatic constituents (extract) are to be separated from (2) the paraffins (raffinate). The extract part is used for the purposes of the invention. Solvents such as furfural, phenol, β, / Γ-dichlorodiethyl ether, nitrobenzene, Duosol (propane and cresol) and sulfur dioxide, preferentially dissolve the aromatic components and the naphthenes and can be used in the extractive treatment of clarified UmIaufolen. According to the invention, furfural is preferably used to increase the aromatic content in the extract, ie to remove the aliphatic and ίο cycloaHphatic constituents.

Further details of typical processes for separating and extracting the circulating oils can be found in U.S. Patents 2,660,552 and 2,882,220. According to these patents, the extraction of the clarified circulating oil for the recovery of the raffinate and not the extract is carried out, indicating another advantage of the invention, namely that the improved impregnating agent according to the invention for from fibers forth sso asked tube members from an inexpensive, readily available material that generally believed to have little commercial value.

Clarified circulating oil, as defined above, is a complex blend of highly aromatic Hydrocarbons and therefore cannot be completely analyzed chemically. The composition of the extract depends on the one hand on the crude oil that is used and on the conditions in the first place Stage carried out distillation, the cracking process, the fractionation, etc. from. A characteristic one Sample of clarified circulating oil extract was obtained by Shell's n-d-m methods with the Analysis of the result given in Table I ("Aspects of the Constitution of Mineral. Oils", K. van Nes et al., Elsevier Publishing Co., Inc., 1951, pp. 318 to 346).

TABLE

ObislOVo 10 to 20 Vo 20 to 30 Vo 30 to 40 Vo sample
40 to 50 Vo 50 to 60 Vo 60 to 70 Vo 70 to 80 Vo Btms. specific weight 0.991 1.025 1.043 1.050 1.071 1.092 1,112 .1,125 1.205 ^ ^70oc , 8 ms / cm3 0.9574 0.9972 1.0122 1.0239 1.042 1.0591 1.0825 Flow point, ⁰ C ..... -3.89 +7.22 12.78 . 18.33 21.11 21.11 15.50 21.11 Ramrnpunkt, ⁰ C .. 168 182 204 196 232 243. 251 254 Color D-155 2— blue green 2 1 2.5 4th 4th viscosity at 99 ° C / SSU .. 32.2 35.3 " 36.5 39.61 44.98 53.7 77.9 107.6 at 38 ° C / SSU .. 48.6 80.8 105.1 Visc-Grav.- 0.996 1.047 1.065 1.06 1.075 1.090 1.109 _M 70 ° C 1.5587 1.5906 1.6021 1.6141 1.6316 ■ 1.6495 1.6690 Aniline point, ⁰ C ... 18.89 20.56 24.16 29.16 32.50 35.00 33.33 Total S content in Weight percent 1.43 2.03 2.21 1.91 1.65 1.63 1.83 1.76 1.03 Total N content in Weight percent 0.025 0.05 0.062 0.067 0.054 0.047 0.062 0.063 0.055 ° / o ring carbon 67.1 66.8 66.9 63.3 61.1 58.4 57.6 * / o more paraffinic carbon 32.9 33.2 33.1 36.7 38.9 41.6 42.4 * / o more aromatic carbon 61.3 66.8 66.9 63.3 61.1 58.4 57.6

Tabel ! (Continuation)

sample Obis 10% 10 to 20% 20 to 30% 30 to 40% 40 to 50% 50 to 60% £ Π ίιίο 7fi 0 / _Λ
OU Dlo l \ j / 0 IVJ slide OU / 0 .D Ulla. % naphthenic 0.0 0.0 carbon 5.8 0.0 0.0 0.0 0.0 Total number The Rings per molecule 1.94 1.97 2.05 2.09 %1 2.04 2.07 Aromatic rings per molecule ,, .. 1.65 1 ₅ 97 2.04 '' 2.09 ■ 2.1 2.04 2.07 Naphthous amounts per molecule 0 , 29 0.0 0.0 O ₅ O 0.0 0.0 0.0 Coal bursts prö molecule 15.8 17.1 17.4 17.5 19.4 19.0 20.7 Molecular weight ... 210 220 225 240 25.Ö 256 265 m

The typical properties of extracts from the heavy ends of clarified circulating oils are given in tables. These properties are for the heavy ends, e.g. B, the 40 to 1 OO volume percent fraction, obtained by distillation to remove the light ends.

Table ΪΙ

Specific gravity 1.151

Specific weight at 15.6 ° C 1.1512

Viscosity SSF at 121 ° C 19.7

Flash point, ° C .... 274

Ramsbottom coal residue

Weight percent, 14.71

Weight percent sulfur 1.23

Penetration at 25 ° C 90

Ring and Ball Softening Point, ⁰ C 39.4

ASTM distillation, ⁰ C
Passed volume percent, ° C

Start of boiling ..; 400

2% 410

5% 418

10% 427

20%: 440

30% 450

40% 460

35

50% 470

60% 487

70%; 505

80% -

100% -

As described above, the heavy ends of the extract are made from or from clarified circulating oil distilled clarified circulating oils, e.g. B. by blowing in an oxygen-containing gas such as air up to a ring and ball softening point within the range of 65 to 120 ° C and preferably from 75 to 80 ° C, after which the material can then be used as an impregnating agent. This . Product is unlike other petroleum resins due to the absence of carbon-containing insoluble Parts that interfere with the impregnation are marked. A pleasant and reliable test for such carbonaceous insolubles is the solubility of the impregnant in quinoline. The oxidized condensation products of the invention of extracts from distilled clarified Accordingly, circulating oils show only a trace of substances insoluble in cliinolin and are preferred 100% soluble in quinoline.

Properties of the impregnating agent produced according to the invention and one that is successful on the market Coal tar derivatives are compared as follows:

Table DI

9 Coal tar product Air-blown extract
of the distilled, clarified
Oil flow
50 to 100 percent by volume Specific weight at 15.6 ° C 1.252 1.190 Ring and ball softening point, ⁰ C 77.8 75.6 Saybolt-Furol viscosity in seconds at 154.4 ° C 37.0 53.0 at 162.8 ° C 19.0 32.9 at 176.7 ° C, 12.0 21.0 • Flash point, ° C 238 268 Quinoline solubility at - 59 ° C,% 97 100

Claims (14)

The advantages of the petroleum derivative according to the invention in comparison with the often widely used coal tar impregnation agents are as follows: 1. The manufacture of the impregnant is stable in that it has to do with the perennial petroleum industry and not to the inconsistent steel production. 2. The impregnating agent can easily be mixed with conventional impregnating agents such as coal tar impregnating agents, be mixed. 3. The absence of phenolic or other harmful fumes prevents physical Influences of phenols and damage to health during manufacture and enables installation the pipes on hot and humid days without burning your hands. 4. The impregnation temperatures no insoluble products are present, the result is a good finish and a smooth pipe ao surface, causing poor flow coefficient and the formation of clots in wastewater and eventual blockage of the tubes does not occur. 5. The low volatility of the impregnating agent allows the vacuum to be increased during the impregnation. 6. The impregnating agent adds less weight to the tube than those available to date Impregnating agent. 7. The low water adsorption of the pipes. 8. Insignificant kerosene solubility of the pipes under the conditions in which they are used will. 9. Great carrying capacity of the pipe. 10. High breaking strength of the pipe. 11. Resistance of the pipe to sulfuric acid, sodium carbonate, sodium sulfate and boiling water. 12. The pipe does not deform or exude pitch when it is at an elevated temperature is held. 13. The high flash point of the impregnation agent offers great safety during the impregnation process. 14. Less volatile products in the impregnation agent. Claim: Process for the production of an impregnating agent for porous pipes, characterized in, that from a crude oil fraction boiling over 315 ° C, the aromatics are extracted in a manner known per se and then be oxidized by blowing with air.