DE961481C - Process for stabilizing heating oils - Google Patents

Description

ISSUED APRIL 4, 1957

St 4916IV c j23 b

The invention relates to a method for stabilizing heating oils derived from cracking processes Shares included. Such heating oils are used in various burner systems as diesel oils or Heating oils used for domestic and industrial needs. Heating oils are made from petroleum after a won a whole range of processes, e.g. B. the direct distillation of crude oil and the thermal and catalytic cracking of petroleum fractions.

It has recently been observed that heating oils which are wholly or partly produced by cracking processes are made, are very volatile. This instability is shown by the fact that after a long period of time Storage, especially at higher temperatures, forms deposits. It also leads to impermanence such heating oils in the relevant system to blockages of the filters, nozzles or fuel supply lines.

Sodium phosphate is known to improve the cleansing effect of sulfonates. the end This behavior cannot be taught to the person skilled in the art about which means are used must in order to stabilize heating oils that contain fractions from cracking processes.

It is also known, used lubricating oils for the separation of foreign matter with an aqueous

To handle solution of trisodium phosphate, to let the material to be treated settle and the to separate the purified oil layer from the aqueous layer. Since the phosphate is insoluble in oil, it works not into the oil, but with the aqueous layer containing the foreign matter removed again.

A multi-component mixture consisting of polycyclic hydrocarbons, such as naphthalene, anthracene, phenanthrene, and also from caustic alkali, a water-soluble one Borate and a water-soluble phosphate such as trisodium phosphate; the water-soluble Additives are dissolved from the water present in the heating oil. The usage of Complexes of a detergent and trisodium phosphate to make this oil-soluble is this one Procedure alien.

It has now been found that the above-mentioned disadvantages are eliminated if at least one Part of the fuel oil is a salt, in particular an alkali or alkaline earth salt, one of phosphorus, antimony, Arsenic or bismuth-derived acid is added and suspended in the oil with the aid of a detergent or as is resolved. The detergent used is preferably Oil-soluble metal soaps or sulfonates, preferably petroleum sulfonates, in particular oil-soluble alkali or Alkaline earth soaps or sulfonates, such as sodium or calcium petroleum sulfonates.

The heating oils that come into consideration here are, for example, hydrocarbon mixtures that lead to more than about 10% Uus products that are produced by thermal or catalytic cleavage are. In particular, it is petroleum fractions that contain more than 10% fission products that meet the ASTM standard D-975-48T for diesel fuels (Class No. i-D to 4-D inclusive) and ASTM standard D-396-48T for heating oils (Class Nos. 1 through 6 inclusive).

A complex compound is likely to form between the metal salt and the detergent, which the Promotes dissolution or suspension of the metal salt in the oil. The complex compound can by Implementation of the components in the oil or before the addition to the oil.

As mentioned, the oil-soluble sodium and calcium petroleum sulfonates are particularly suitable as detergents. In the case of the alkaline earth sulfonates, the sulfonates of barium, calcium, strontium and magnesium are particularly preferred. Other detergents that can be used are e.g. B. the metal soaps of the C ₁₆ - to C ₂₄ fatty acids or naphthenic acids. However, these and other products which can also be used per se do not appear to be as effective as the petroleum sulfonates of the metals indicated.

Of the salts of the acids of phosphorus, arsenic, antimony and bismuth, the salts of phosphoric acids, especially the sodium salts, are particularly recommended. Na ₃ PO ₄ seems to be the most suitable sodium phosphate, although Na ₂ HPO ₁ , NaH ₂ PO ₄ , Na ₄ P ₂ O ₇ and Na ₃ PO _{3 also} stabilize heating oil. The present invention is described in particular with regard to the use of trisodium phosphate, Na ₃ PO ₄ . The specified salts can be used in anhydrous as well as in hydrate form.

The salts of the acids of arsenic, bismuth, antimony or phosphorus are needed for heating oil only add very small amounts. When referring the proportion to be used to anhydrous salt, this can be about 0.0001 up to o, r weight percent.

According to the preferred embodiment of the invention, the salt of the relevant acid of phosphorus, arsenic, bismuth or antimony is added to the heating oil in the form of a complex with an alkali or alkaline earth metal petroleum sulfonate which contains about 2 to 20% of the salt. In this case, about 0.0005 to 5 percent by weight of this complex can be used. Preferably, however, the specified complex in amounts of about 0.005 is to o.o2 ° / _0, based on the weight of the oil used. Since the amounts given are based on the anhydrous salts, the amounts by weight, if the salt is used in hydrate form, have to be corrected according to the water content. The complex compound is obtained by adding an 'aqueous solution of the salt, e.g. B. sodium phosphate, to oil-soluble petroleum sulfonate, e.g. B. sodium or calcium sulfonate. The mixture is then heated to about 149 ° to completely dehydrate it. In this case the phosphate forms a true solution in the oil. There is no separation of the salt from the oil as long as a critical concentration of phosphate in the sulfonate is not reached. A sodium sulfonate concentrate (e.g. 65% sulfonate, 35% oil) can _{absorb "up to about 20% Na 3} PO ₄ · 12H ₂ O. With a 30% calcium sulfonate concentration, approximately the same amount of salt can be absorbed.

In order to enjoy the advantages and applicability of the χ To show the present invention proposed mixtures, some test results are given below. For this purpose a Commercial fuel oil used, which is made from a mixture of 20 to 30% of a catalytic Cleavage obtained product, 50 to 40% of a product obtained by thermal cleavage and 30% of untreated crude oil. The key figures for this oil are the following:

no table 1

Density 15.6 ° 0.8545 '

Color (Day Robinson) n-3/4

Flash point, ⁰ C 70.0

Sulfur (° / ₀ ) 0.56

Aniline point, ° C 54.4

Neutralization number 0.07

Distillation, ⁰ C

Start of boiling 172.2

io ° / "215.6

50% 251.1

90% 302.2

End boiling 331.0

Carbon residue

at 10% soil content (%) 0.82

The sodium petroleum sulfonate used in these experiments was a concentrate of sodium petroleum sulfonate of a molecular weight of about 467 in a naphthenic lubricating oil in one Weight ratio of about 50% - three attempts were made to determine the key figures for the fuel oil mixtures to investigate. In two of these attempts

the deposited amounts were determined by iostündiger storage at 99 ⁰ and after storage at 66 ° I4tägiger. In the third experiment, the rusting effect of the fuel oil mixture to which 10% water was added was determined, both in the aqueous phase and in the oil phase. The results of these tests are given in Table 2.

Table 2 Resistance of heating oils containing a sulfonate-phosphate complex

relationship concentration mg of insolubles per 600 g 14 days at
65.6 ° Rust formation * oily phase Na ₃ PO ₄ - 12H ₂ O added
Na petroleum sulfonate in percent by weight 16 hours at
98.9 ° 22nd aqueous phase no 0.0 0.01 45 6th no no 0.067 0.01 12th 3 no no 0.133 0.01 5 I. no no 0.20 0.01 2 2 no no 0.266 0.01 2 2 no no 0.40 0.01 2 - no -. 0.0 0.0075 39 - - - 0.067 0.0075 12th - - - 0.133 0.0075 3 - - - 0.20 0.0075 3 - - - 0.266 0.0075 3 - - - 0.40 0.0075 4th - - - 0.0 0.005 30th - - - 0.52 ■ 0.005 6th 21 - no no addition - 32 strong

Mild steel strips kept in contact with the oil sample, which contained 10% water, for 52 days at room temperature. 95

As indicated in Table 2, the sodium phosphate which is present in the oil acts in the form of a complex with sodium petroleum sulfonate, stabilizing at all specified concentrations on the Heating oil. In addition, the complex of sodium phosphate and sodium sulfonate eliminated the corrosive effect of the heating oil in the aqueous phase It is It is of particular importance that, according to the values given, sodium petroleum sulfonate is inherently unstable of the heating oil is not eliminated, but a combination of sodium phosphate and sodium petroleum sulfonate is required necessary.

Further attempts were made to investigate the behavior of salts of other phosphoric acids investigate. The results are shown in Table 3. The listed salts of the relevant Phosphoric acids were tested in the above-mentioned commercial heating oil. In any case it was the relevant salt of phosphoric acid to commercial heating oil in the form of a 50% concentrate of the phosphate incorporated into a lubricating oil carrier. It can be seen from Table 3 that each of the specified Salts, which were made soluble by sodium petroleum sulfonate, which effectively stabilized heating oil, as can be seen from the stability test after 16 hours.

Table 3 Effect of various phosphates in the complex

phosphate Ratio of salt * to
Na petroleum sulfonate Concentration of
Additive
in percent by weight 16 hours at 99 °
mg of insolubles
600 g each Na ₅₁ HPO ₄
NaH ₂ PO ₄ -H ₂ O
(NH ₄ ) ₂ HPO ₄
Na ₄ P ₂ O ₇
Na ₃ PO ₄ -12H ₂ O
Sulfonate alone
uninhibited 0.08
0.08
0.08
0.14
0.20
0.00 0.01
0.01
0.01
0.01
0.01
0.01 I.
I.
3
14th
I.
30th
32

* The salts were used in equivalent concentrations.

Further attempts were made to investigate the effectiveness of salts, their Acids are derived from other elements of group V, again the same as identified above Fuel oil was used. Each of the salts in question was given to heating oil in the form of its complex with sodium petroleum sulfonate added. The key figures obtained are shown in Table 4 below specified.

Table 4
Sodium salts of oxygen acids of the V group

salt Ratio * salt to
Na petroleum sulfonate Concentration of
Additive in percent by weight Stability test
(16 hours at 99 °)
mg of insolubles per 600 g of oil Sodium arsenite
Sodium arsenate
Sodium bismuth
Sulfonate alone
no inhibitor O, l6
O, O8
0.14
0.00 0.01
0.01
0.01 I.
5
28
30th
32

Based on equivalent concentrations.

It can be seen from the table that each of the salts investigated has a stability-increasing effect. It is However, note that the salts of arsenic acids work better than the salt of bismuth acid seem.

Finally, tests were carried out in which the complex of sodium sulfonate described above and sodium phosphate the fuel oil in combination with an alkaline earth metal alkyl phenol sulfide was added. Barium isooctylphenol sulfide was added as the sulfide. The. obtained values are compiled in Table 5 below. They show that the stability of a heating oil is through this ternary addition can be increased.

Table 5

Sulphonate-phosphate complex * in combination with barium isooctylphenol sulphide

additive
Weight percent active ingredients

0.004% Ba-phenol sulfide

+ O ₁ Oi% sulfonate phosphate .. 2

+ 0.01% sulfonate 36

+ 0.005% sulfonate phosphate 2

4- 0.005% sulfonate 27

0.002% Ba-phenol sulfide

+ O ₁ Oi% sulfonate phosphate .. 1

-f- ο, οΐ ° / ₀ sulfonate 30

No inhibitor ....: 32

* Ratio Na ₃ PO ₄ . 12H ₂ O is the same as Na petroleum sulfonate. 0.20.

According to the invention, an alkali, alkaline earth or ammonium salt of an acid of phosphorus, Antimony, arsenic or bismuth in small quantities

Stability test

(16 hours at 99 ⁰ )

mg of insolubles

600 g of oil each

with the help of a detergent added to a heating oil that contains fractions originating from cracking processes. The heating oil can also contain other compounds besides alkaline earth alkylphenol sulfides, namely the other commonly used additives are added.

Claims (10)

PATENT CLAIMS: 1. Process for stabilizing heating oils which contain fractions originating from cracking processes, characterized in that at least part of the heating oil is a salt, in particular a Alkali or alkaline earth salt, an acid derived from phosphorus, antimony, arsenic or bismuth added and with the help of a detergent in the Oil is suspended or dissolved. 2. The method according to claim 1, characterized in that that a phosphate, arsenate, arsenite, antimonate or bismuthate is used as the salt. 3. The method according to claim 1 and 2, characterized characterized in that the salt used is trisodium phosphate. 4. The method according to claim 1 to 3, characterized in that the salt in amounts of 0.0001 to 0.1 percent by weight, based on oil, is used. 5. The method according to claim 1 to 4, characterized in that the detergent used is oil-soluble Metal soaps or sulfonates, preferably petroleum sulfonates, especially oil-soluble alkali or Alkaline earth soaps or sulfonates, such as sodium or calcium petroleum sulfonates, are used. 6. The method according to claim 1 to 5, characterized in that the salt and the detergent mixed together before adding to the oil. 7. The method according to claim 1 to 6, characterized in that the salt and the detergent the oil as a complex, in particular 0.0005 to 5, preferably 0.005 to 0.2 percent by weight per day added to the complex compound. 8. The method according to claim ι to 7, characterized in that a complex is used which contains 2 to 20% salt. 9. The method according to claim 1 to 8, characterized in that there is a detergent organometallic compound used. 10. The method according to claim 1 to 9, characterized "characterized in that an alkali or alkaline earth metal alkylphenol sulfide is also added to the oil. References considered: U.S. Patents Nos. 2,137,727, 1,302,094; Ellis, The Chemistry of Petroleum Derivatives, 1934, Vol. I, p. 1024. 609579/468 8.56 (609 853 3.57)