DE949588C - Process for refining petroleum products - Google Patents

Description

ISSUED ON & SEPTEMBER 1956

GERMAN PATENT OFFICE

PATENT LETTERING

Jfc 949 CLASS 23b GROUP 1-os INTERNAT. CLASS CIOg

C 7740 IVc123b

Andre Gislon, Paris,

have been named as inventors

Compagnie Franqaise de Raffinage, Soc. An., Paris

Process for refining petroleum products

Patented in the territory of the Federal Republic of Germany from June 18, 1953 Patent application published March 22, 1956 Patent granted published August 30, 1956

is used

The invention relates to a process for refining petroleum products by oxidation of the in these contained mercaptans to disulfides, as it is known under the name "sweetening".

The German patent 832 312 describes a process for "sweetening" petroleum products by catalytic Oxidation of mercaptans using organometallic scissors compounds (chelates). Under The aquo-dicobalt salt of bis-disalicylal-ethylenediimine has proven to be particularly effective in these compounds shown.

According to the invention, these chelates are first formed and oxidized in the petroleum product to be refined then immediately the mercaptans. For this purpose one leaves in the petroleum containing mercaptan Alkyliminophenol, in particular certain alkyliminophenols, react with a metal salt. The condensation products of an o-oxybenzaldehyde have proven to be suitable alkyminophenols proved to be an apathetic diamine.

Among the suitable metal salts are the metal salts of the eighth group of the periodic Systems and especially the cobalt salts.

So you can z. B. dissolve the alkyliminophenol in the petroleum and this mixture with an aqueous Solution or better an aqueous-alcoholic or alcoholic solution of the selected metal salt in Bring touch. The alkyliminophenol itself can be used as an alcoholic solution or in an aromatic Dissolved hydrocarbons are added.

The metal salt can be an organic metal salt soluble in hydrocarbons. The procedure

is carried out in a neutral, but preferably in an alkaline medium.

The reaction must be carried out in the presence of air or an oxygen-containing gas, but below Under certain circumstances, the oxygen dissolved in the petroleum is sufficient.

Several examples are given below to illustrate the invention, in which various Alkyliminophenols used with cobalt salts

will. ". . ,

Example ι

... * ΐ * * Zu / i Jjp * Wkbenzin with a boiling range up to 200 ⁰ ^ A- ^: Sn ^ ' ^J erSerii ^ sulfur content of 0.033% in the form of; ^ MereapÄ one adds 33 mg of one by condensation ^; . * Jiw>n>S; ä | jcylaldehyde and ethylenediamine are added to A ^ ylifa & ophehols and stirred in the air for 1 hour with 10% methyl alcoholic cobalt acetate solution. Then the mixture is left to stand. The mercaptan content then decreases rapidly over time and has practically disappeared after 24 hours, as can be seen from Table 1:

Table 1
(Reagent: AlkyHminophenol + Cobalt Acetate)

Mercaptan sulfur content

Initial value 0.033 percent by weight

after 3 minutes 0.028

- 60 - 0.015

4 hours 0.011

- 24 - 0.003

It is advantageous to use a metal salt soluble in gasoline, e.g. B. salts of fatty acids, such as stearates, oleates, naphthenates or alkyl phthalates.

Example 2

In 11 boiling range Iraq gasoline containing mercaptan up to 200 ° different amounts of disalicylal-propylene-dimin were used and cobalt oleate dissolved. The AlkyHminophenol was partly in toluene, partly in methanol dissolved added. In a number of experiments the amount of alkyliminophenol and of cobalt oleate varied, and moreover, the effect of alkali on the reaction was increased by addition different amounts of 10% aqueous or methyl alcoholic sodium hydroxide solution to some of the samples examined.

The test conditions and results are summarized in Table 2.

From Table 2 it can be seen that the addition of the AlkyHminophenols in alcoholic solution is more favorable has an effect than in toluene solution, and also that the decrease in the mercaptan content in an alkaline medium occurs more quickly than in a neutral medium, so that in the case of alkaline reaction conditions the for Sweetening within a given time required reagents are applied in significantly smaller quantities can be.

Tabel

Trial number

5 6th 7th 8th 9 IO 1000 1000 1000 1000 1000 1000 0.237 0.252 0.252 0.252 0.252 0.252 0.040
toluene 0.032
CH ₃ OH 0.024
CH ₃ OH 0.016
CH ₃ OH 0.008
CH ₃ OH 0.016
CH ₃ OH 10.2 8.16 6.12 4.08 2.04 4.08 20 ecm
NaOH
Metha
nol
10% 50 ecm
NaOH
aqueous
10% 0.033
0.000 0.035
0.005
0.003 0.035
0.009
0.006 0.035
0.015
0.014 0.035
0.023
0.020 0.035
0.004 - 0.001 0.004 0.012 0.020 0.002

Fuel quantity,
ecm

Mercaptan sulfur, g ...

Disacylalpropylenediimine, g ....

Solvent..
cobalt

(as oleate), mg
additional
Reagent

Decrease of the
Mercaptan sulfur,
Weight percent S
Time: 0 hours
ι hour
3 hours.

5 hours

6 hours

20 hours

24 hours

1000 1000 1000 0.237 0.237 0.237 0.040
toluene 0.040
CH ₃ OH 0.040
CH ₃ OH 10.2 10.2 10.2 50 ecm
NaOH
aqueous
10% 0.033 0.033
0.008 0.033
0.004 0.025 - 0.000 0.014 0.000 -

1000

0.237

0.040 CH ₃ OH

10.2

20 ecm NaOH methanol 1000

0.252

0.008

: h ₃ oh

0.033 0.000 2.04

25 ecm NaOH aqueous 10%

0.035

0.004 0.004 las

The cobalt salt selected in the context of the invention by no means needs one that is soluble in hydrocarbons Salt such as the above-mentioned salts of fatty acids, naphthenic acids or alkylphthalic acids other organic cobalt compounds, especially the alcoholates, enolates, Phenates, alkyl phenates, etc. can be used.

The cobalt salt can be used alone or in solution in an excess of alcohol, phenol or alkylphenol etc. are added, these substances stabilizing the gasoline in a manner known per se act.

Example 3

11 in gasoline is dissolved (average Orient) from the final boiling point of 205 ⁰ with a sulfur content of 0.025 percent by weight in the form of mercaptan 0.040 g Disalicylal-propylenediimine, then 0.15 g of a mixture of cresol and Kobaltkresolat with a content of 0.0102 g of cobalt. The mixture is stirred in the presence of air and left to stand. After 3 hrs. The mercaptan sulfur is only o OO6 ° / _0th

Example 4

11 gasoline with 0.035% mercaptan sulfur is reacted with 1.6 cc of an i ° / _o by weight methyl alcohol solution of Disalicylal-äthylendiimin and 0.0177 § cobalt acetylacetonate, corresponding to 0.0021 g Kob'alt mixed. After 6 hours the mercaptan sulfur content has fallen to 0.04%.

The statement that the alkyliminophenols by condensation of o-oxybenzaldehyde and aliphatic Diamines are to be understood in the broadest sense, i.e. such bases can also then be used if other substituents are present in the o-oxybenzaldehyde nucleus, the art the diamine chain can be any.

The following example particularly gives the use of a condensation of o-oxybenzaldehyde and Di-aminodipropylamine

(NH ₂ - (CH ₈ ), - NH _ (CH ₂ ) ₃ - NH ₂ ) obtained alkyliminophenols. Example 5

To 11 gasoline with 0.033 per cent mercaptan sulfur 0.020 g of disalicylal dipropylaminodiimine and an amount of cobalt oleate corresponding to 0.00485 g of cobalt added. It is stirred with 50 ecm of an aqueous solution of 10% sodium hydroxide solution. After 3 hours it is Mercaptan sulfur content decreased to 0.004%.

It has been found that the condensation products of aromatic compounds of the structure o-oxyaldehyde, the main representative of which is o-oxybenzaldehyde is, with aromatic or hydroaromatic cyclic diamines with the cobalt salts Enter coordination compounds that are also formed in the petroleum products themselves and a sweetening effect of petroleum products by oxidizing the mercaptans.

These connections correspond to the general one

^Formula , OH HO.

Ar;

= N-Ar'-N = HC

Here, Ar denotes a simple or substituted benzene or naphthalene nucleus and Ar 'denotes a simple one or, substituted cyclic aromatic or hydroaromatic nucleus.

The refining process according to the invention can be applied to all other petroleum distillates in addition to gasoline or use cracked gasoline such as heavy gasoline, white spirit or luminous oil.

Tabel example

Petroleum product

lot

origin

Boiling limits

Mercaptan sulfur, ° / ₀
Treated with
Alkyliminophenol ...

Amount, g
Cobalt ..

petrol

10 1 Iraq

up to 205 ° 0.030

Disalicylalphenylenediimine ¹ )

0.19

0.04 g as oleate

petrol

10 middle

Orient up to 200 °

0.03

Disalicylal

naphthylene

diimin ² )

0.22

Oleat gasoline

il

middle
Orient

200 °

0.033

Disalicylalcyclohexylene

diimin ³ )
. 0.185
Oleat

Solvent ι m ³

120 to 200 ° 0.038

Disalicylal

propylene

diimin

600 ecm

solution

by Co-Oleat

in luminous oil

6.8 g Co / 1

¹ J Made from salicylaldehyde and o-phenylenediamine.

² ) Made from salicylaldehyde and 1,8-diaminonaplithalin.

³ ) Made from salicylaldehyde and iya-diaminocyclohexane.

Luminous oil ι m ³

200 to 250 ⁰ 0.031

Disalicylalpropylenediimine

0.04

0.010 g co-stearate

Table 3 continued

6th 7th example
8th 9 IO 5
NaOH 50 cm ³ io%
NaOH
in H ₂ O + CH ₃ OH
3
<0.002 5
0.003 3
<0.002 2 1 5%
aqueous-
alcohol.
NaOH
5
0.002 io% ige
aqueous
NaOH
20th
0.009 ¹⁰ mercaptan sulfur
after treatment,
hours % s

In the context of the invention, the process can also be carried out continuously. You can z. Am Enter the petroleum to be sweetened into a mechanical mixer in which a small amount of an alkylaminophenol is dissolved and a dilute alkaline aqueous, or aqueous-alcoholic solution and a small one Allow the amount of petroleum containing a small amount of a metal compound of the 8th group to flow in. If the oil contains too little dissolved oxygen, air is blown in. The one formed in the mixer The emulsion is then transferred to a settling tank. Here the emulsion separates into one alkaline aqueous-alcoholic or aqueous phase, which is returned to the mixer, and that sweetened product that is continuously withdrawn from the sedimentation tank.

Table 4 gives the test results with continuous operation with two different Alkyliminophenols again.

Tabel

concentration

Example 11

Throughput speed

concentration

Example 12

Throughput speed

NaOH in a mixture of equal parts of the volume

Water and methanol

Salicylalpropylenediimine dissolved in Iraqi gasoline
Salicylal-o-phenylenediimine, dissolved in

. ₀ Iraq gasoline

Co-oleate or ricinoleate dissolved in Iraqi gasoline
Initial mercaptan sulfur content,%
Mercaptan sulfur in the treated product,
0 /

0.08 g / l

0.2 g Co / 1 0.030 100 1 / hour.
1000 1 / hour

10 1 / hour

<0.002 10%

0.010 g / l

0.2 g Co / 1
0.030

<0.001

100 1 / h

1000 1 / hour 10 1 / hour

A modification of the process is that the alkyliminophenol in the to be refined Hydrocarbon dissolves and this solution on a solid, the metal salt-bearing carrier in the Cycle, as the following example indicates.

Example 13

It is dissolved in gasoline with a boiling point of up to 200 ° and a content of 0.033% mercaptan sulfur 0.040 g per 1 disacylalethylene diimine and 1% methanol. This gasoline is circulated through a carrier made of activated carbon loaded with cobalt nitrate. The solution treated in this way is washed with water or dilute sodium hydroxide solution. From the suds the methanol is recovered in a known manner. The mercaptan sulfur content of the gasoline is up 0.003% down.

According to the described embodiments of the method according to the invention one obtains in some Felling colored products, which are cleared by settling. In any case, a filtration leads via decolorizing agents or simply washing with water or diluted lye to the goal, whereby colorless products are obtained which are free from any metal compound.

For some gasolines, the effectiveness of the process can be improved by using the product to be treated traces of free sulfur iao or added to labile sulfur-releasing compounds. The same result is also achieved by the Presence of very small amounts of alkali metal sulfide in the aqueous or aqueous-alcoholic 'phase obtained, as long as one works in an alkaline medium. If the latter does not contain or only insufficiently sulfur,

According to the invention, a small amount of sulfur can be added to the product to be treated right at the beginning or add it during treatment. After the end of the treatment, no trace is clear or contain labile sulfur in the petroleum product.

Claims (6)

Patent claims: ίο i. Process for refining petroleum products by catalytic oxidation of the mercaptans by means of organometallic scissor compounds (Chelates), characterized in that the chelates in the product to be treated are formed. 2. The method according to claim 1, characterized in that that the reaction in the petroleum between an alkyliminophenol, especially a condensation product one possibly in the core ao substituted o-oxybenzaldehyde with an aliphatic Diamine, e.g. B. ethylene or propylenediamine, di-amino-dimethylamine, di-amino-dipropylamine, a cyclic, aromatic, or hydroaromatic diamine with simple rings (like benzene or cyclohexane) or fused rings (like naphthalene or hydronaphthalene) or branched chains and a metal salt, in particular a salt of a metal of the 8th group of the periodic table, preferably a cobalt salt. 3. The method according to claim 1 and 2, characterized in that the petroleum product to be refined after addition of the alkyliminophenol with an aqueous, aqueous-alcoholic or alcoholic Solution of the metal salt either on its own or in the presence of an excess of acid, alcohol, phenol is brought into contact, the metal salt being one in hydrocarbons soluble salt of an organic acid, e.g. B. a stearate, oleate, naphthenate or alkyl phthalate, or an organic compound of cobalt, e.g. B. an alcoholate, enolate, phenolate or alkyl phenate is used. 4. The method according to claim 1 to 3, characterized in that the alkyliminophenol in alcoholic solution or dissolved in an aromatic hydrocarbon is used. 5. The method according to claim 1 to 4, characterized in that the sweetening in neutral or alkaline medium. 6. The method according to claim 1 to 5, characterized in that for continuous implementation of the process an aqueous-alcoholic sodium or potassium hydroxide solution with the to be cleaned Petroleum product is emulsified, the latter being an alkyliminophenol and a soluble cobalt salt contains and the emulsion by decanting continuously into an aqueous-alcoholic solution that is recycled and a purified petroleum product is separated. ©; 0S b98 / 430 3.56 (609 615 9.56)