DE1470306C3 - Process for the production of condensation products - Google Patents

Description

The invention relates to the production of condensation products that prevent clogging of the sieve, Sediment formation, oxidation and metal activity in hydrocarbon fuels have a stabilizing effect.

It is well known that liquid hydrocarbon fuels such as heating oils, diesel oils and gasoline have a tendency to either after long periods of storage or under the conditions of operational use to show adverse properties. For example, fuel oils have proven to be unstable in High temperature environments and they tend to foul heat exchanger tubes and cause clogging of screens and clogging of pipes. Sediment formation is one other common occurrence. In gasolines as well as in fuel oils there is oxidation and occurrence metal activity is also undesirable phenomena, the elimination of which is sought. Accordingly is an additive that stabilizes such fuels and prevents sediment formation, clogging of sieves, Oxidation and metal activity protects, extremely desirable.

The invention relates to a process for the preparation of condensation products, which is characterized in that an alkenyl succinic acid or its anhydride with salicylaldehyde and a polyamine of the formula H ₂ N (- R - NH) ,, - H, in which R is an ethylene or propylene radical and η is an integer from 1 to 6.

It can be seen that there must be at least two carbon atoms in the alkenyl radical but there is no real upper limit to the number of carbon atoms it contains. The alkenyl succinic anhydrides and the alkenyl succinic acids are for purposes of the invention interchangeable. Accordingly, if the term "alkenyl succinic anhydride" is used below is used, it should be noted that this term includes both the alkenylsuccinic acids and includes their anhydrides. Examples of the alkenyl succinic anhydride component include tetrapropenyl succinic anhydride, nonenyl succinic anhydride and octadecenyl succinic anhydride.

Generally, alkenyl succinic anhydrides containing 8 to 35, and preferably 9 to 18 carbon atoms contained in their alkenyl group, most advantageously used in the process according to the invention. Processes for the preparation of the alkenylsuccinic anhydrides are known, the most favorable method being comprised the reaction of an olefin with maleic anhydride. A more detailed description the alkenyl succinic anhydrides suitable for use in the preparation of the condensation products according to the invention and their Manufactured in U.S. Patent 2,638,450.

The polyamine reactant used in the manner noted above with the alkenyl succinic anhydride and salicylaldehyde reactants has the formula H ₂ Ni-R-NH) ₇₁ -H, where R is ethylene or propylene and η is an integer of 1 to 6 means. examples for

ίο The polyamine reactants are among others Ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and dipropylenetriamine.

The polyamine reactant is preferably used in an amount of 1 to 2 mol per mole of alkenyl succinic anhydride is used, and the salicylaldehyde reactant is used in the additive composition preferably used in an amount of 1 to 10 moles per mole of alkenyl succinic anhydride.

The condensation product prepared according to the present invention is added to the fuel oil in a small amount in order to bring about an improvement thereof. In general, the additive composition can range from 2.85 to 570 kg / 100 m ³ . and preferably vary from 2.85 to 71.2 kg / 1000 m ^{3 of} the fuel oil; If this information is expressed in percent by weight, then the concentration of the additive composition can vary from 0.00025 to 0.1 and preferably from 0.00025 to 0.01 percent by weight of the fuel oil.

The following examples illustrate the method according to the invention. The comparison values show the effectiveness of the compounds in improving the properties of liquids Hydrocarbon fuel oils.

Example I.

40 g _^(2/3 mol) of ethylene diamine was gradually added at room temperature under stirring to 88.7 g ⁽¹ J ₃ moles) of tetrapropenyl succinic anhydride, 192 g of the xylene and 100 cm ^{3 of} benzene were diluted. The reaction was exothermic and the temperature rose rapidly to 65 ⁰ C. Upon completion of the addition, the mixture at 75 to 80 ° C over a period of 30 minutes was stirred. To this reaction mixture were added salicylaldehyde at room temperature under stirring, then 81.3 g (/ ₃ MoI ^2). The resulting mixture was then maintained at 95 to 100 ° C over a period of 3 hours at reflux and then maintained at 130 ^c C, until no more water could be collected (ie, after a period of 2 hours). The amount of water collected was 20 cm ³ (theory 18 cm ³ ). The resulting reaction product was found to contain about 50 percent by weight xylene; The product was clear and fluid at 70 ° C. For the analysis of this reaction product was found to have a nitrogen content of 4.71 ° / ₀ versus a calculated value of 4.87 percent by weight.

B e i s ρ i e 1 2

49.3 g ⁽² Z ₃ moles) corresponding to 61.6 g 8O ° / _O propylenediamine sodium was gradually added to a mixture of 88.7 g (V ₃ moles) of tetrapropenyl succinic anhydride and 201 g of xylene at room temperature under

Stir added. This mixture was then ^{stirred at 95 °} C. for a period of 2 hours. ^{81.3 g (2} / _: mol) of salicylaldehyde were then gradually added to this reaction mixture at room temperature with stirring. The resulting mixture was then slowly heated to reflux temperature (145 ° C) and held at that temperature until no more water could be collected (this was after a period of 3 hours). The amount of water collected was 29 cm ³ (theory 30 cm ³ ). The reaction product obtained was filtered through clay; the final product obtained contained about 50 percent by weight xylene and was dark brown in color, clear and flowable at room temperature. In the analysis of this reaction product was found to have a nitrogen content of 4.9 ° / _0, compared with a calculated value of 4.5 weight percent.

Example3

51.5 g (0.5 mole) of diethylenetriamine all-ΓΛ were gradually added to a mixture of 66.5 g (0.25 mol) - added ^v tetrapropenylsuccinic anhydride and 165 g of xylene as a diluent at room temperature with stirring, followed by the addition of 61 g (0.5 mol) of salicylaldehyde diluted with 50 cm ^{3 of} benzene. The mixture was gradually heated to reflux at 135 ° C and held at that temperature until no more water could be collected (ie after a period of 3 hours). The amount of water collected was 15 cm ³ (theory 13.5 cm ³ ). The reaction product was filtered through clay and the final product obtained contained about 50 weight percent xylene and was clear and flowable at room temperature. In the analysis of this reaction product was found to have a nitrogen content of 5.87 ° / ₀ versus a calculated value of 6.5 weight percent.

Example 4

73 g (0.05 mol) of triethylenetetramine gradually became a - at room temperature with stirring. Mixture of 66.5 g (0.25 mol) tetrapropenylbem -% ..? stinic anhydride and 187 g of xylene added; subsequently 61 g (0.5 mol) of salicylaldehyde, diluted with 50 cm ^{3 of} benzene, were added. This mixture was gradually heated to reflux at 135 ⁰ C and maintained at this temperature until no more water could be collected (ie, after a period of 2 hours). The amount of water collected was 15 cm ³ (theory 13.5 cm ³ ). The resulting reaction product was then filtered through clay and the final product obtained contained about 50 weight percent xylene and was clear and flowable at room temperature. In analyzing this final reaction product showed a nitrogen content of 7.23 ° / ₀ versus a calculated value of 7.7 weight percent.

Example 5

94.5 g (0.5 mol) of tetraethylene pentamine were gradually added at room temperature with stirring to a mixture of 66.5 g (0.25 mol) of tetrapropenylsuccinic anhydride and 208 g of xylene; subsequently 61 g (0.5 mol) of salicylaldehyde, diluted with 50 cm ^{3 of} benzene, were added. The mixture was gradually heated to reflux at 135 ° C and held at that temperature until no more water could be collected (this was after a period of 3 hours). The amount of water collected was 15 cm ³ (theory 13.5 cm ³ ). The reaction product obtained was filtered through clay; the final product obtained contained about 50 percent by weight xylene and was clear and flowable at room temperature. When analyzed, this reaction product showed a nitrogen content of 3.4 percent by weight.
Example 6

49.3 g ⁽² mol I ₃₎ corresponding to 54.8 g of 90 ° / ₀ sodium propylenediamine was gradually added at room temperature with stirring to a mixture of 75 g ⁽¹ I ₃₎ Norienylbernsteinsäureanhydrid and 187 g of xylene, followed by addition of 81.3 g _^(2/3 mol) of salicylaldehyde. The resulting mixture was slowly heated to reflux at a temperature of 142-145 ⁰ C and maintained at this temperature, until no more water could collected (which was for a period of 3 hours). The amount of water collected was 23 cm ³ (theory 23.5 cm ³ ). The reaction product was then filtered through clay; the final product obtained contained about 50 percent by weight xylene and was clear and flowable at room temperature. Upon analysis, this final reaction product showed a nitrogen content of 6.02 percent versus a calculated value of 5.0 percent by weight.

B e i s ρ i e 1 7

37 g (0.5 mol) corresponding to 41 g of 90 ° / ₀ sodium was gradually propylenediamine (0.25 mole) of octadecenyl succinic anhydride and 147 g of xylene were added at room temperature with stirring to a mixture of 62.5 g; subsequently 61 g (0.5 mol) of salicylaldehyde were added. The resulting mixture was then slowly heated to reflux temperature at 142-145 ° C and held at that temperature until no more water could be collected (ie after a period of 3 hours). The amount of water collected was 17.5 cm ³ (theory 17.5 cm ³ ). The resulting reaction product was then filtered through clay; the final product obtained contained about 50 percent by weight xylene and was clear and flowable at room temperature. On analysis, this reaction product showed a nitrogen content of 4.67% compared to 4.71% by weight

percent. :

The condensation products produced by the process according to the invention are liquid Hydrocarbon fuel oils, including the distillate fuel oils, d. H. Petrol, fuel oils and heating oils, valuable properties of the type indicated above. The fuel oils are hydrocarbon fractions, which have an initial boiling point of at least 38 ° C and an end boiling point not higher than 399 ° C and boil essentially continuously over their distillation range. Such fuel oils are commonly known as distillate fuel oils. It should be noted, however, that this designation is not is limited to straight run distillate fractions. The distillate fuel oils can be straight run distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils or mixtures of straight run distillate fuel oils, naphthas and the like with cracked de-

trade stillat materials. In addition, such fuel oils can according to known technical Methods are treated, e.g. B. acid or alkali treatment, hydrogenation, solvent refining, Clay treatment, etc.

The distillate fuel oils are also characterized by their relatively low viscosities, pour points, and the like. marked.

Among the fuel oils come in particular the Fuel oils No. 1, 2 and 3 are considered, which are used for heating purposes and as diesel oils, as well as the jet fuel oils or jet fuels. The household heating oils generally comply with the regulations which are given in ASTM Specifications D 396-48T. Regulations for diesel oils are in the ASTM specification D 975-48 T defined. Typical jet fuel oils are in the military specification MIL-F-5624B defined.

In the case of the gasolines produced by the addition of condensation products prepared according to the invention are improved, they are mixtures of hydrocarbons with an initial boiling point between 24 and 57 ° C and a final boiling point between 121 and 232 ° C. As is well known, motor gasoline can consist of straight run gasoline or, as is more common, a mixture of two or more Cuts or materials, including straight run material, catalytic or thermal reformate, cracked material, alkylated natural gasoline and aromatic hydrocarbons.

Clogging of the sieve

The anti-clogging properties of a fuel oil are determined in the following way: The test is performed using a Sunstrand V-3 or S-1 domestic fuel oil burner pump with a closed 100-mesh (mesh) Monel metal sieve carried out. About 0.05 percent by weight, of course fuel oil sediment formed from fuel oil, water, dirt, rust and organic sludge exists are mixed with 10 1 of the fuel oil. The mixture is by means of the pump for 6 hours the sieve circulates. Then the sludge deposit on the sieve is washed down with normal pentane and filtered through a tared Gooch crucible. After drying, the material is in the Gooch crucible with a 50:50 (volume) acetone-methanoi mixture washed. All of the organic sediment is obtained by evaporating the pentane and the acetone-methanol filtrates. Drying and weighing the Gooch crucible gives the amount of inorganic sediment. The sum of the Organic and inorganic deposits on the sieve can be expressed as the recovered amount in muligrams can be specified or converted to the percentage of clogging of the sieve.

The uninhibited test fuel oil was represents a mixture of 60% distillate material obtained from a continuous catalytic cracking, and 40 ° / ₀ straight-run distillate material which had a boiling range of about 160 to 338 degrees C and a typical fuel oil No. 2,.

There were mixtures of the condensation products obtained according to the examples with the above test fuel oil described and subjected to the screen clogging test. The results are listed in Table I.

Table I.
Clogged fuel oil screen

Condensation product
according to the example Concentration
tion
kg / 1000 m " Siebver
constipation
% Non-inhibited fuel oil
mixture
+ Example 1
4- Example 2
+ Example 3
+ Example 5
+ Example 6
+ Example 7 0
142.5
, 71.3
71.3
71.3
28.5
71.3 100
30th
8th
20th
25th
5
10

sedimentation

The test that was used to determine the sedimentation properties of the fuel oils is the Storage test at 43.3 ° C. This test uses a 500 ml sample of the fuel oil to be tested is introduced into a convection oven, which over a period of time is held at 43.3 ° C for 12 weeks. Then the sample is removed from the oven and cooled. The chilled Sample is filtered through a tared asbestos filter (Gooch crucible) to remove any insoluble components to remove. The weight of such components in mg is given as the amount of sediment. A sample of the pure, non-inhibited oil is used together with the tested fuel oil mixture Subject to test. The effectiveness or performance of a fuel oil that contains an inhibitor will by comparing the weight of sediment formed in the inhibited oil with the weight on sediment formed in the uninhibited oil is determined.

The condensation products obtained in the above examples were converted into the above Test fuel oil was mixed in and the mixtures were subjected to the 43.3 ° C storage test. The test results, which the mixed fuel oils and comparing the uninhibited fuel oils are given in Table II.

Table II
Fuel oil storage test - 43.3 ° C, 12 weeks

Condensation product
according to the example Concentration
tion
kg / 1000 m ³ sediment
mg / 1 Uninhibited
Fuel oil mixture
Uninhibited
Fuel oil mixture
+ Example 2
Uninhibited
Fuel oil mixture
Uninhibited
Fuel oil mixture
+ Example 6
Uninhibited
Fuel oil mixture
Uninhibited
Fuel oil mixture
+ Example 7
Uninhibited
Fuel oil mixture 0
28.5
0
71.3
0
71.3
0 77
62
8th
3
8th
4th
69

Gasoline storage test

This test was applied to the amount of Gumzunahme both in a fuel mixture comprising 100 ° / ₀ catalytically cracked component, 0.79 cm ³ tetraethyl lead (TEL) per liter and contained within a boiling range of 38 boiled to 204 ⁰ C, as also the same gasoline mixture that

also contained one of the condensation products obtained according to the examples. To Storage at 43.3 ° C for 16 weeks was the amount of gum gain according to determined by ASTM test D 381. The test results, which the non-inhibited gasoline and the same gasolines, but containing the condensation products obtained according to the examples, compare are given in Table III.

Table III
Gasoline storage test

Condensation product according to the example Weeks at
43.3 ° C Conc
tration
kg / 1000 m ³ ASTM Gum
increase
mg / 100 ml Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l
Non-inhibited gasoline + 0.79 cm ³ tetraethyl lead / l + example 1
Non-inhibited gasoline - + 0.79 cm ³ tetraethyl lead / l Γ
Non-inhibited gasoline + 0.79 cm ³ tetraethyl lead / l + example 2
Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l
Non-inhibited gasoline + 0.79 cm ³ tetraethyl lead / l + example 3
Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l
Non-inhibited gasoline + 0.79 cm ³ tetraethyl lead / l + example 4
Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l
Non-inhibited gasoline + 0.79 cm ³ tetraethyl lead / l + example 5
Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l 16
16
16
16
16
16
16
16
16
16
16 0
28.5
0
14.3
0
28.5
0
28.5
0
14.3
0 42.7
1.9
42.7
1.7
19.7
2.5
19.7
1.4
2.6
1.6
1.4

Gasoline storage test with copper contained and also 0.2 mg copper naphthenate

included per liter as a metal catalyst. The test-

The same test method was used as the results which mix the uninhibited gasolines and the same ones described above in connection with the gasoline storage test 35, as described in the examples, with gasoline containing the same gasoline condensation products, the 0.79 cm ^{3 of} tetraethyl lead (TEL) per liter are given in Table IV.

Table IV
Petrol storage test with copper

Condensation product according to the example - Example 1 Weeks at Conc
tration ASTM Gum
increase kg / 1000 m ³ mg / 100 ml Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 16 0 75.0 Uninhibited gasoline - Example 2 + 0.79 cm ³ tetraethyl lead / l + 0.2 mg copper naphthenate / 1 - \ 16 14.3 5.1 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 16 0 75.0 Uninhibited gasoline - Example 3 + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 -i 16 8.6 3.9 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 16 0 21.5 Uninhibited gasoline - Example 4 + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 H 16 28.5 12.6 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 16 0 26.5 Uninhibited gasoline - Example 5 + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 H 16 28.5 8.1 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 16 0 21.5 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 H 16 28.5 1.5 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l + 0.2 mg Cu naphthenate / 1 16 0 30.4

309 533/489

Claims (1)

Claim: Process for the preparation of condensation products, characterized in that an alkenylsuccinic acid or its anhydride is mixed with salicylaldehyde and a polyamine of the formula H ₂ Ni-R-NH) ₇₁ -H, in which R is an ethylene or propylene radical and η is an integer of 1 to 6 means converts.