DEC0010278MA - - Google Patents

Description

Authority en turn!

FEDERAL REPUBLIC OF GERMANY

Registration date: November 18, 1954. Advertised on December 27, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

CLASS 23b GROUP toe INTERNAT. CLASS CIOg

C 10278 IVc / 23b

Andre Gislon, Paris, Joseph Quiquerez and Jean Daniel Maurin, Gonfreville-L'Orcher, Seine-Inferieure (France)

have been named as inventors

Compagnie Frangaise de Raffinage, Soc. An., Paris

Representative: Dipl.-Ing. H. Leinweber, patent attorney, Berlin-Zehlendorf West, Goethestr. 30th

Process for sweetening petroleum products

The priority of the application in France of December 19, 1953 has been claimed

In German patents 832 312, 949
describes a general process for refining petroleum products and various embodiments of that process. Basically, this process consists in sweetening the products, ie oxidizing the mercaptans usually contained in them, in the presence of organometallic shear compounds (chelates) as catalysts, such as those obtained by reacting certain Schiff bases with a metal salt, in particular in the presence of cobalt scissors compounds derived from Schiff bases obtained by condensation of salicylaldehyde with a diamine.

609 738/339

C 10278 IVc / 23b

Of the embodiments of this general sweetening method, the following are particularly important to notice:

'The gap compounds the petroleum products to be treated or they can be added to finished ^v * is generated in situ. The diamine used to form the Schiff base can be aliphatic, cyclic, aromatic, or hydroaromatic. The scissors connection can in the presence of a solvent, such as. B. an alcohol, a ketone, a phenol, a fatty acid, etc., or in the form of an aqueous or aqueous-alcoholic dispersion. The petroleum product can be continuously brought into contact with an excess of the scissors compound in such a dispersion which is recycled after separation, or an exactly sufficient amount of a solution can be added to the product to be treated. the scissors link, in which case the sweetening of the product will gradually take place during its further storage.

It should be noted that the oxygen dissolved in the petroleum product to be treated often causes oxidation the mercaptans are sufficient without the need to blow air.

The present invention relates to the general method described and can be applied to all embodiments of the procedure.

The invention consists in that the oxidation of the mercaptans in the petroleum products according to the above procedures described in the presence of a lead salt.

Namely, it has been found that the addition of a lead salt to the organic scissors compound is several Offers advantages. On the one hand, it is easier to obtain complete sweetening of such products; on the other hand you achieve a considerable saving in the scissor connection used.

The inventive method can be used in different. 40 those modifications are carried out, which as to the conditions under which the lead salt is added to the petroleum product or scissors compound as to the method of forming the latter or the combination of the two Differentiating factors from each other.

The most important embodiments are described below, but the invention does not apply to them is limited.

The lead salt can be selected from those salts that are soluble in hydrocarbons; So an organic salt comes into consideration Phenolate, mercaptide, etc.

The lead salt can compound the hydrocarbon to be treated together with the scissors, optionally in the presence of a solvent for the scissors connection.

Schiff's base and cobalt salt can be added to the petroleum product together with the lead salt, which serve to form the scissors connection in situ.

In the latter case, you can work in the presence of an alkaline aqueous solution, which is essentially has the purpose of neutralizing the acid released by the formation of the scissors connection.

However, the stoichiometric required for this neutralization is not absolutely necessary Limit the amount of caustic soda, but you can, especially when running the reactions in continuous Operation, with an excess of caustic soda over that in a given instant Freedom set amount of acid work.

Furthermore, one can use the petroleum product mixed with the scissors connection - be it that this is called has added such, be it that they are added by successive addition of Schiff base and Has generated cobalt salt in situ - possibly in the presence of a solvent for the scissors connection with an alkaline solution in contact bring containing a lead salt, d. H. in the end with an alkaline plumbite solution.

In another embodiment, the petroleum product containing a lead salt can be with a treat aqueous or aqueous-alcoholic dispersion of the scissors compound, which latter in the aqueous or aqueous-alcoholic medium by adding a Schiff base and a cobalt salt can be generated in situ in solution in a dispersant.

The following examples, to which the invention is not limited, illustrate various embodiments the same and show the advantages achieved according to the invention numerically Comparative values on:

95 Example 1

A mixture of distillate and cracked gasoline with a boiling range of 40 to 200 ° and a mercaptan sulfur content of 0.024 percent by weight was mixed with the following additives in six parallel tests: a) 0.30 g / l cresol with a 10% lead content in the form of Cresolate, made by dissolving black lead in cresol; b) 0.30 g / l cresol with a content of 10% of the scissors compound of cobalt and disalicylal-propylenediimine-1,2; c) 0.50 g / l cresol with a content of 10 ° / ₀ of the same scissors linkage; d) 0.20 g / l of cresol with a content of 10% of the same scissors compound; e) 0.30 g / l cresol containing 6.6% of the same scissors compound and 6.6% lead; f) 0.30 g / l cresol with a content of 6.6% of the same scissors compound and 10% lead.

All petrol is left for storage. This takes place in those gasolines that use the scissors connection contain a progressive decrease in the mercaptan content with simultaneous formation a precipitate of cobalt and / or lead oxides instead, which can be easily removed by filtration leaving a gasoline that is completely free of metal compounds.

Table I shows the change in mercaptan content of the various samples over the course of 24 hours and the stability of the gasolines obtained according to the various treatment instructions in comparison with untreated (h) or cresol-inhibited (g) petrol.

738/339

C 10278 IVc / 23b

Table I.

Chelate Additives Pb Mercaptan sulfur content . after By ι g Stability, g / 1 g / i 24 hours Chelate Induction Ver O 0.03 TO ° / o oxidized period* search 0.03 Cresol O Beginning 0.022 sulfur 0.05 g / i O ° /. 0.003 G; 132 (a) 0.02 0.30 O 0.024 0.000 142, (b) 0.02 0.30 0.02 0.024 0.010 : 5, o - (C) 0.02 0.50 0.03 0.024 0.000 4, o - (d) 0 0.20 O 0.025 0.000 5.4 150 (e) 0 0.30 O 0.024 0.024 8.6 - (f) 0.30 0.025 0.024 9, o 132 (G) 0.30 0.024 58 (H) O 0.024

* The induction period was calculated according to ASTM regulation D 525-49.

You can see that lead alone is practically ineffective, and that only then can you use the scissors connection Complete sweetening is obtained when it is added in sufficient quantities (in the investigated Examples on the order of 0.05 g / l), while one by the combination of scissors connection and lead a complete sweetening already at a consumption of 0.02 g / l scissors compound receives.

It can also be seen from Table I that the application the method according to the invention ■ causes stabilization of the gasoline.

Example 2

A luminous oil of Iraqi origin (boiling range 196 to 257 ⁰ , D. = 0.795) and a gas oil of Iraqi origin (boiling range 192 to 371 ⁰ , D. = 0.838) are according to Example I with 0.30 g / l cresol with a content of 10 ° / ₀ bis-disalicylal-ethylenediamino-dicobalt and 10% lead treated in the form of lead cresolate.

Table II shows the advantage of the presence of lead, which leads to increased effectiveness of the Scissors connection with respect to the sweetening leads.

35 Chelate
g / l Table II Pb
g / l Mercaptansc
to
Beginning
% sulfur content
after'
24 hours
° / o By ig
Chelate
oxidized
sulfur
G Treated
product
40 0.30
0.30
0.30
0.30 Additives
Cresol
g / l O
0.03
O
0.03 0.030
0.030
0.030
0.030 0.012
0.000
: 0.015
0.000 4.7
8.0
4.3
8.6 Iraq luminous oil
45 Iraq gas oil 0.03
0.03
0.03
0.03

After sweetening, the products are made with 0.1% active earth or by washing with 20% sulfuric acid discolored and are then completely free of metal compounds.

Example 3

a) A distillate gasoline from Iraq is mixed with 3 ccm / 1 of methanol with a content of 10 g / l salicylal-propylenediimino-cobalt added.

b) A sample of gasoline is ^{mixed with 1} Z _{40 of} its volume of the same gasoline, which, however, has been washed with plumbite. In this way, a gasoline is obtained in which ¹ Z _{40 of} the mercaptans are in the form of lead mercaptide. This mixture is mixed with 3 cc / l of methanol with a content of 10 g / l of the cobalt-shear compound.

c) A sample of gasoline is filled with 0.014 g / l lead in the form of lead naphthenate and then with 3 ccm / l Methanol containing 10 g / l of the cobalt scissors compound offset.

The gasoline is left to store for 24 hours, filtered through sand and it is found that im Case of the gasolines treated with the cobalt scissors compound in the presence of lead a complete Sweetening has taken place (Table III).

609 738/339

C 10278 IVc / 23b

Table III

Methanol Additives Pb Mercaptan sulfur after
24 hours Pb as a mercaptide ccm / 1 Chelate g / 1 TO
Beginning Vo Pb as
Naphthenate 3, o
3, o g / 1 O
0.023 Vo 0.003
0.000 (a)
(b) 3, o 0.03
0.03 0.014 PP
bb
K) K)
Oi Oi 0.000 (C) 0.03 0.025

Example 4

This example concerns the formation of the cobalt scissors bond in situ.

A distillate gasoline from the Middle East is mixed with the following additives in parallel tests: a) 0.015 g / 1 disalicylal-propylenediimine-i, 2 and 0.0032 g / 1 cobalt in the form of cobalt naphthenate; b) 0.015 g / 1 disalicylal-propylenediimine-i, 2, 0.0032 g / 1 cobalt (as naphthenate) and 0.047 sweet lead as mercaptide; c) 0.015 g / 1 disalicylal-propylenediimine-i, 2, 0.0032 g / 1 cobalt (as naphthenate) and 0.028 g / 1 lead as naphthenate. ,

After 24 hours, nitration is carried out and the mercaptan content is determined.

The results, compiled in Table IV, demonstrate the advantage of the addition of lead, the effectiveness the scissor compound formed in situ from Schiff base and cobalt salt is increased.

Table IV

Pb Additives Co Mercaptan sulfur after By ι g g / 1 Salicylal (as naphthenate) to 24 hours Chelate
oxidized O diimin g / 1 Beginning Vo sulfur 0.047 g / 1 0.0032 Vo 0.015 G (a) 0.028 0.015 0.0032 0.025 0.003 4.0 (b) 0.015 0.0032 0.025 0.004 8.8 (C) 0.015 0.025 8.4

Example 5

A distillate gasoline from the Middle East containing no free sulfur is mixed with them Reagents as in Example 4, but in the presence of 25 ccm / 1 10% sodium hydroxide solution. The results obtained with various amounts of the additives are shown in Table V.

Table V

Additives Salicylal Co NaOH Mercaptan sulfur after By ι g diimin (as naphthenate) io ° / " to 24 hours Chelate
oxidized lead g / 1 g / 1 g / 1 Beginning Vo sulfur g / 1 0.0075 0.00l6 25th Vo 0.010 G O 0.0075 0.00l6 25th 0.025 0.003 12.0 0.047 0.0075 0.00l6 25th 0.025 0.002 17.5 0.028 0.0150 0.0032 25th 0.023 0.0005 I6.5 0.028 0.015 0.0032 25th 0.025 0.004 10.0 O 0.025 8.4

The combination of lead with the cobalt scissors compound enables the mercaptan content to be reduced to a copper number of 4 without additional consumption of the scissors connection and even results a sweetener.

In addition, a comparison with Example 4 shows the beneficial effect of the sodium hydroxide solution.

Example 6

A gasoline, to which 7.5 g / m ^{3 of} disalicylal-propylenediimine-i, 2 and 1.6 g / m ^{3 of} cobalt in the form of cobalt acetylacetonate are added one after the other, is mixed in a mixer with a tenth of its volume io ° / ₀ iger sodium hydroxide solution brought into intimate contact, in which 3.5 g / 1 black lead dissolved

738/339

Claims (18)

C 10278 IVc / 23 b. Air is blown in at the same time. The aqueous phase is drawn off in a separator and recycled into the mixer. In this way, 70 l of gasoline with an initial mercaptan sulfur content of 0.025 percent by weight were treated with 100 ecm of plumbite-containing sodium hydroxide solution. The gasoline obtained in this way had a copper number of 3. EXAMPLE 7 An aqueous dispersion of the cobalt scissors compound of 1,2-disalicylal-propylenediimine is prepared by adding stoichiometric amounts of sodium hydroxide solution, disalicylal-propylenediimine-1,2 and cobalt nitrate of a mixture of 90 Percent by volume of water and 10 percent by volume of a solution of a sodium alkylarylsulfonate acting as a wetting agent are added. A stable 1% aqueous dispersion of the scissors compound is obtained. 11 Iraq gasoline with a boiling point of 200 °, a density of 0.720 and a mercaptan sulfur content of 0.025 percent by weight is shaken for 3 minutes with 3 ecm of the described 1% dispersion of the scissors compound and then left to rest. After 24 hours the mercaptan sulfur content has dropped to 0.012%. A parallel test carried out with the same reagents, in which the gasoline had previously been mixed with 0.03 g / l Pb in the form of lead cresolate, gave a gasoline after 24 hours which only contained 0.002% mercaptan sulfur. Example 8 An aqueous-alcoholic solution of the cobalt scissors compound of disalicylal-propylenediimine-1,2 is prepared, which contains 6 g / l scissors compound and 100 ccm / l methanol. 1. With 250 ecm of this solution, 701 Iraq distillate gasoline with a mercaptan sulfur content of 0.025 ° / _{0 is} treated in continuous operation in the presence of air. After the treatment, a gasoline containing 0.007% mercaptan sulfur is obtained. In this experiment, 1 g of scissors compound oxidized 5.4 g of mercaptan sulfur. 2. With 250 ecm of the same aqueous-alcoholic solution of the scissors connection, the same result Amount of petrol treated after 0.03 g / l of lead had been added in the form of lead cresolate. In this way, 1001 could run gasoline Operation be completely sweetened, with ι g of the scissors compound oxidized 12 g of sulfur. All of the above exemplary embodiments are based on the addition of a lead salt to the reactive products. However, it is also within the scope of the invention to use one for sweetening according to the present method Use apparatus that contains lead parts. Indeed, when executing the sweetening process according to the invention under certain operating conditions such lead parts to form lead salt, which then plays the same role as when it is in the reacting substances Would have been added in the form of a salt. PATENTANSI'R Q CHE: 1. A method for sweetening petroleum products, characterized in that the oxidation the mercaptans in the simultaneous presence of an organometallic scissors compound (chelate) and of a lead salt. 2. The method according to claim 1, characterized in that that one as organometallic shear compound is that of cobalt with a Schiff's base is used, which is obtained by condensation of an aromatic oxyaldehyde, such as salicylaldehyde, with a diamine. 3. The method according to claim 1, characterized in that that the organometallic compound in the petroleum product in situ by adding an in Hydrocarbons soluble cobalt salt, such as. B. a fatty acid salt, an alcoholate, a Phenate, etc., and one by condensing an aromatic oxyaldehyde with a diamine obtained Schiff's base is formed. 4. The method according to claim 1, characterized in that that one adds a lead salt to the scissors connection, which is in hydrocarbons is soluble. 5. The method according to claim 1, characterized in that that the scissors link the petroleum product in solution in one with the latter miscible solvents such as an alcohol, ketone, phenol, fatty acid, etc., together with a lead salt soluble in hydrocarbons, e.g. B. an organic salt, phenolate or Mercaptide, adds. 6. The method according to claim 1, characterized in that that you do this beforehand with a cobalt salt, a Schiff base and a lead salt brings mixed petroleum product into contact with an alkaline solution. 7. The method according to claim 1, characterized in that that the petroleum product previously mixed with a cobalt salt and a Schiff base brought into contact with an alkaline solution containing a mineral salt of lead. 8. The method according to claim 1, characterized in that that the petroleum product previously mixed with a lead salt with an aqueous dispersion of a Cobalt scissors joint treated. 9. The method according to claim 1 and 8, characterized in that the dispersion of the Scissors connection by adding a cobalt salt and a Schiff base to the aqueous Solution of a surfactant produces. 10. The method according to claim 1, characterized in that that the petroleum product previously mixed with a lead salt with an aqueous alcoholic dispersion of a cobalt scissors connection treated. 11. Solution for sweetening petroleum products according to the method of claim 1, characterized in that it is an organometallic Contains scissors compound (chelate) and a lead salt. 609 738 / 33J C 10278 IVc / 23b 12. Solution according to claim ii, characterized in that the organometallic scissors connection is that of cobalt with a Schiff base, which is formed by condensation of a aromatic hydroxyaldehyde with a diamine. 13. Solution according to claim 11, characterized in that that the lead salt is a salt soluble in hydrocarbons, e.g. B. a salt of an organic Acid, a naphthenate, phenate, etc. is. 14. Solution according to claim 13, characterized. draws that the solvent is a mixed solvent for the scissors connection and for is the lead salt, which is also miscible with hydrocarbons and from the group of Alcohols, ketones, phenols, fatty acids, etc. is selected. 15. Solution according to claim 11, characterized in that that it consists of a solution of lead cresolate and the Schereny compound of cobalt with a disalicylal diimine in cresol. ■. ■ ■ 16. Solution according to claim 11, characterized in that that it consists of two mutually usable solutions, one of which A solution of a Schiff base according to claim 12 and the other a mixed solution of an in Cobalt salt soluble in hydrocarbons and a lead salt soluble in hydrocarbons is. 17. Solution according to claim 16, characterized in that that the solution of the Schiff base by a stoichiometric amount of an alkali hydroxide is made alkaline in the ratio of 2 moles of alkali per mole of disalicylal diimine. 18. Solution according to claim 17, characterized in that that the solution of the Schiff base is an alcoholic solution of a disalicylal diimine and an alkali alcoholate. © 609 738/339 12. 56