DE1470306B2 - PROCESS FOR MANUFACTURING CONDENSATION PRODUCTS - Google Patents

Description

3 4

Stir added. This mixture was then collected on could (which was stirred for a time-95 ⁰ C over a period of 2 hours. Space of 3 hours). The amount of collected water for this reaction mixture was then 15 cm ³ (theory 13.5 cm ³ ). The ermählich 81.3 g _^(2/3 moles) of salicylaldehyde at room maintained reaction product was filtered through clay; temperature added with stirring. The resulting end product contained about 50 weight-giving mixture was then slowly heated to the reverse percent xylene and was clear and flowable at room flow temperature (145 ° C.) and at this temperature. On analysis this showed reaction temperature held until no more water collected could become a nitrogen content of 3.4 weight (that was after a period of percent.

3 hours). The amount of water collected io examples
was 29 cm ³ (theory 30 cm ³ ). The reaction product obtained was filtered through clay; the obtained 49.3 g of _^(2/3 mole) corresponding to 54.8 g of 90 ° / ₀ sodium ProEndprodukt contained about 50 weight percent xylene, propylenediamine were gradually at room temperature and was colored dark brown, clear and flowable at stirring to a mixture of 75 g ( ¹ I ₃ ) None-room temperature. In the analysis of this reaction showed 15 nylbernsteinsäureanhydrid and 187 g of xylene were added, ligation product has a nitrogen content of 4.9 ° / _0, counter, followed by addition of 81.3 g _^(2/3 moles) Salicylüber a calculated value of 4, 5 weight aldehyde. The resulting mixture slowly became percent. heated to reflux at a temperature of 142 to 145 ° C Example 3 and held at this temperature until no. 20 more water could be collected (that was

51.5 g (0.5 mol) of diethylenetriamine were all- after a period of 3 hours). The amount

gradually to a mixture of 66.5 g (0.25 mol) of the collected water was 23 cm ³ (theory

Tetrapropenyl succinic anhydride and 165 g xylene 23.5 cm ³ ). The reaction product was then through

filtered as a diluent at room temperature under clay; the final product obtained contained about

Stir added, followed by the addition of 61 g of 25 50 weight percent xylene and was clear and fluid

(0.5 mol) of salicylaldehyde, diluted with benzene ³ 50 cm. capable at room temperature. When analyzed showed

The mixture was gradually brought to reflux at this final reaction product a nitrogen gas

Heated to 135 ° C and held at this temperature until the content reached 6.02 ° / ₀ compared to a calculated value

no more water could be collected (i.e. from 5.0 percent by weight,
after a period of 3 hours). The amount of 30

collected water was 15 cm ³ (theory 13.5 cm ³ ). Example 7
The reaction product was filtered through clay, and

the final product contained about 50 weight 37 g (0.5 mol) corresponding to 41 g of 90 ° / ₀ sodium Proprozent xylene and was clear and flowable at room propylenediamine were gradually at room temperature temperature. In the analysis of this reaction showed 35 with stirring to a mixture of 62.5 g (0.25 mol) product has a nitrogen content of 5.87 ° / ₀ over octadecenyl succinic anhydride and 147 g of xylene to a calculated value of 6.5 weight percent. admitted; subsequently 61 g (0.5 mol) of salicylaldehyde were added. The resulting mixture was

Example 4 then slowly to reflux temperature at 142 bis

40 145 ⁰ C heated and held at this temperature until

73 g (0.05 mol) of triethylenetetramine were no longer collected (ie gradually at room temperature with stirring to one after a period of 3 hours). The amount of the mixture of 66.5 g (0.25 mol) of tetrapropenyl amber collected water was 17.5 cm ³ (theory stinic anhydride and 187 g of xylene added; after 17.5 cm ³ ). Following the resulting reaction product was 61 g (0.5 mole) of salicylaldehyde, which was then filtered through clay; the resulting final dilution with 50 cm ^{3 of} benzene was added. This mixture product contained about 50 percent by weight xylene and was gradually heated to reflux at 135 ° C and was clear and flowable at room temperature. Could be held at the at this temperature until no more water Analysis of this reaction product showed a stick collected (ie, after a period oxygen content of 4.67 ° / ₀ over 4.71 Gewichtsvon 2 hours). The amount of collected water 50 percent. . . >. ". ■;., -.;. '..
was 15 cm ³ (theory 13.5 cm ³ ). The resulting reaction product according to the process of the invention was then filtered through clay, the condensation products given give liquid and the final product obtained contained about 50 Ge hydrocarbon fuel oils, including the weight percent xylene and was clear and flowable in distillate fuel oils, i.e. gasoline, fuel oils and heating oils , Room temperature. In the analysis of this final 55 valuable properties of the valid reaction product specified above exhibited a nitrogen content of Art. The fuel oils are Kohlenwasserstofffrak-7.23 ° / ₀ versus a calculated value of 7.7 overall functions, an initial boiling point of at least weight percent. 38 ° C and a final boiling point not higher than 399 ° C of Example 5 and substantially continuously above theirs

60 distillation area boiling. Such fuel oils

94.5 g (0.5 mol) of tetraethylene pentamine were all- are generally known as distillate fuel oils, gradually forming a mixture of 66.5 g (0.25 mol) at room temperature with stirring. Tetrapropenyl amber is restricted to straight run distillate fractions. In the case of stinic anhydride and 208 g of xylene added; After oiling the distillate fuel, it can be straightforward 61 g (0.5 mol) of salicylaldehyde, ver 65 run distillate fuel oils, catalytically or thermally thinned with 50 cm ^{3 of} benzene, were added. The mixture of cracked (including hydrocracked) distillate was gradually heated to reflux at 135 ⁰ C and fuel oils or mixtures of straight-run Destillatbei kept this temperature, fuel oil until no more water, naphthas u. Like. Cracked with 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 desfillate fuel oils are also characterized by their relatively low viscosities, pour points and the like. marked.

Among the fuel oils, in particular, the fuel oils No. 1, 2 and 3 come into consideration, which are used for heating purposes and as diesel oils, as well as jet fuel oils or jet fuels. The household heating oils generally conform to the regulations set out in ASTM specifications D 396-48 T. are specified. Regulations for diesel oils are defined in ASTM specification D 975-48 T. Typical Jet fuel oils are defined in the military specification MIL-F-5624B.

In the case of the gasolines produced by the addition of condensation products prepared according to the invention be improved, it is a mixture 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 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 screen. About 0.05 percent by weight, of course fuel oil sediment formed from fuel oil, water, dirt, rust and organic sludge are mixed with 101 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-methanol 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 milligrams 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 160-338 ⁰ 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 ³ Siebver
constipation
% Non-inhibited fuel oil
mixture
+ Example 1
+ 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. In this test, a 500 ml sample of the fuel oil to be tested is placed in a convection oven introduced, which is kept at 43.3 ° C for a period of 12 weeks. Then it will be removed the sample from the oven and cooled. The cooled sample is passed through a tared asbestos filter (Gooch crucible) filtered to remove insolubles. The weight of such components in mg is given as the amount of sediment. A sample of the pure uninhibited oil is taken together subjected to the test with the tested fuel oil mixture. Effectiveness or performance of a fuel oil containing an inhibitor is calculated by comparing the weight of sediment that is in the inhibited oil has been formed 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 ⁰ C, 12 weeks

Condensation product
according to the example
50 Concentration
tion
kg / 1000 m ³ sediment
mg / 1 Uninhibited
Fuel oil mixture
Uninhibited
55 fuel oil mixture
+ Example 2
Uninhibited
Fuel oil mixture
Uninhibited
60 fuel oil mixture
+ Example 6
Uninhibited
Fuel oil mixture
Uninhibited
65 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% catalytically cracked component, 0.79 cm ³ containing tetraethyl lead (TEL) and per liter within a boiling range of 38-204 ⁰ C boiling, as well as 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 7
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 obtained according to the examples with the same gasoline condensation products containing gasoline, 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 + 1 mg Cu-naphthenate / ^J 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 -f- 0.79 cm ³ tetraethyl lead / l + 0.2 mg copper naphthenate / 1 - 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 copper naphthenate / 1 - 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 copper naphthenate / 1 - 16 28.5 1.5 Uninhibited gasoline + 0.79 cm ³ tetraethyl lead / l -f 0.2 mg Cu naphthenate / l 16 0 30.4

309 533/489

Claims (1)

1 2 products according to the invention are suitable, and their Claim: ': Manufacture can be found in the USA patent specification 2,638,450. Process for the preparation of condensation The polyamine reactants, which in the precursors, characterized in the 5 standing manner indicated with the alkenyl succinic acid or its acid anhydride and salicylaldehyde reactants anhydride with salicylaldehyde and a polyamine is used, has the formula H ₂ N (-R -NH) jj-H, of the formula H ₂ N (—R - NH) ₇₁ - H, in which R where R is an ethylene or propylene radical and η is an ethylene or propylene radical and η is an integer from 1 to 6 means. Examples of numbers from 1 to 6 means, implements. The polyamine reactants are among others Ethylenediamine, propylenediamine, diethylenetriamine, _ ^ ___ triethylenetetramine, tetraethylenepentamine and di- propylenetriamine. The polyamine reactant is preferred The invention relates to the preparation of 15 wise in an amount of 1 to 2 moles per mole of alkenyl Condensation products used against clogging of the sieve, succinic anhydride, and the salicylic Sediment formation, oxidation and metal activity in aldehyde reactants is in the additive feed Hydrocarbon fuels have a stabilizing effect. composition preferably in an amount from 1 to It is known that liquid hydrocarbon fuels have 10 moles per mole of alkenylsuccinic anhydride materials, such as heating oils, diesel oils and petrol, which NEI uses. The condensation produced according to the invention under the conditions of operational use is likely to show disadvantageous properties to the fuel oil in a small amount. For example, fuel oils have been added to improve the same In general, the additive composition can be found to be high temperature environments and they range from 2.85 to 570 kg / 100 m ³ and tend to foul heat exchanger tubes preferably from 2.85 to 71.2 kg / 1000 m ³ des Burning and clogging of sieves and clogging of oil vary; if one expresses this information accordingly to cause pipes. Sediment formation is expressed in percent by weight, then the concentration can be another frequently encountered phenomenon. In gasolines with an additive composition from 0.00025 to 0, 1 and, as well as in fuel oils, oxidation and the build-up are preferably from 0.00025 to 0.01 G Metal activity also varies in weight percent, which is undesirable for the fuel oil. phenomena whose elimination is sought. The examples below illustrate this according to an additive that fuels such a process according to the invention. The comparison values stabilized and against sedimentation, Siebver- show the effectiveness of the compounds with regard to Protects constipation, oxidation and metal activity, improving the properties of liquids extremely desirable. Hydrocarbon fuel oils. The invention is a method for Production of condensation products, which there- Example 1
is carried in that an alkenyl succinic acid or anhydride with salicylaldehyde and 40 40 g _^(2/3 mol) of ethylene diamine was gradually a polyamine of the formula H ₂ N (- R - NH) _n - H, at room temperature under stirring, to 88, 7 g (V ₃ mol) in which R is an ethylene or propylene radical and η is a tetrapropenylsuccinic anhydride, which, together with 192 g, is an integer from 1 to 6. Xylene and 100 cm ^{3 of} benzene were diluted, added. It can be seen that at least two carbon atoms are present, and the temperature atoms in the alkenyl radical must be present, 45 rising rapidly to 65 ° C. On completion of the addition, but there is no real upper limit on how the mixture became at 75 to 80 ° C for a period of the number of carbon atoms contained therein. stirred for 30 minutes. For this reaction, the alkenyl succinic anhydrides and alkenyl then 81.3 g _^(2/3 mole) of salicylaldehyde were mixture succinic acids of the invention at room temperature under stirring are added for the purpose. These are interchangeable. If the resulting mixture was then used at 95 to 100 ° C, the expression "alkenylsuccinic acid anhy- over a period of 3 hours at reflux drid" is used, it must be ensured that this is maintained and then at 130 ° C held until no more pressure could be collected both the alkenylsuccinic acids and water (ie after including their anhydrides. Examples of the alkenyls a period of 2 hours). The amount of succinic anhydride component under water collected was 20 cm ³ (theory 18 cm ³ ), the tetrapropenyl succinic anhydride of which was found to contain about 50 percent by weight of xylene; acid anhydride. the product was clear and flowable at 70 ° C. In general, alkenyl succinic anhydrides, analysis showed this reaction product to have a carbon content of 8 to 35 and preferably 9 to 18 carbon content of 4.71% compared to a calculated atom in its alkenyl group, at the advantageous value of 4.87 percent by weight,
most adherent used in the process according to the invention. Process for the preparation of the alkenyl succinic acid- Example2
anhydrides are known, the most favorable method involves the reaction of an olefin with maleic acid 65 49.3 g ⁽² mol of J ₃₎ corresponding to 61.6 g of 80 ° / ₀ sodium Proanhydrid. A more detailed description pylenediamine gradually became a mixture of the alkenylsuccinic anhydrides, which were used to convert 88.7 g ( ¹ _{l 3} mol) of tetrapropenylsuccinic acid in the preparation of the condensation anhydride and 201 g of xylene at room temperature