DE2558907A1 - PROCESS FOR PRODUCING A SURFACE-ACTIVE, BIODEGRADABLE CHEMICAL COMPOUND AND THE USE OF IT - Google Patents

Description

Process for the production of a surface-active, "biodegradable chemical compound, and the use thereof

The present invention relates to new organic dispersants, which are biodegradable and non-toxic and in particular Used to disperse fatty substances and hydrocarbons in an aqueous medium. You are very special suitable for dispersing hydrocarbon surfaces that are random are spread out on the surface of water ^ and for the purification of all contaminated with fatty substances and / or petroleum fractions Surfaces.

With regard to pollution in the sea, it should be said that transport and the handling of hydrocarbons cannot be carried out without certain incidental losses which are more or less considerable which causes a noticeable pollution of the watery environment and thereby of the coasts and rivers.

This pollution that is caused by

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fabric surfaces on the surface of water shows, "brings a large number of drawbacks with it. Besides the aesthetic disadvantages - which one must not trivialize ₉ since they affect the economic viability of tourism in the countries - r.an. observes significantly more serious disadvantages ₉ the harm the biological balance of the aqueous environment: on the one hand the hydrocarbon surfaces, which are spread out in more or less thick layers on the water surface, stick to living things such as birds and fish as well as plankton and cause them to die by suffocation or poisoning - on the other hand they have that effect They counteract gas exchange, in particular by preventing the dissolution of oxygen in water, which is obviously detrimental to the development of underwater animals, and these areas also pose a threat to bird species that get their food from the sea.

One of the ways to remove the hydrocarbon surfaces on the surface of the water is to disperse the Surface with the help of detergents - to effect an emulsion of hydrocarbons to form in the water. This procedure has the advantage, on the one hand, of an even layer to destroy, which counteracts the dissolution of the oxygen in water and on the other hand by the dispersion of the hydrocarbon in fine particles that are more sensitive to degradation by the To make milieu. This natural breakdown on chemical, photo-chemical or biochemical pathway is very slow; the factors which limit the degradation, are of decreasing importance: the accessibility of the oxygen, the size of the

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serstoff / water, survival and growth (-etc nitrogen, phosphorus ... ") of a microflora (algae, bacteria, molds) with the consumption of biogenic elements, the use of the detersive ₉ ium the hydrocarbons to be dispersed, it would allow to remove the first restrictive factors. However, the use of the detergents is not without danger neither for the aquatic flora and fauna nor for the microorganisms of the water.

Regarding the pollution of the soil, it can be said that it is partial the storage and processing of hydrocarbons that never run without losses, in particular when cleaning the various containers; however, the main cause is the processing of oils and fuels in the Petrol stations and the use of industrial oils, their outflow is poorly controlled.

This pollution appears at the level of the ground * but it does is made even more considerable by the fact that all hydrocarbon residues eventually get carried away in the rivers

The present invention has the purpose of creating new dispersing, biological Produce degradable and non-toxic compounds that also reduce the biological runoff of hydrocarbons favor. .

it is known that - to ensure good biodegradation of detergents or dispersants - the aqueous environment, by using the detergent or the dispersant,

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must be sufficiently rich in nitrogen. If this isn't the pail, it is advisable to add the necessary nitrogen to the aqueous medium at the same time as the detergent or dispersant lsiten «,

In certain terms according to the prior art it is known the nitrogen by adding a nitrogen compound run in the detergent itself. However, this solution is sufficient In fact, the nitrogen compound, which is independent Clay from the detergent molecule is far away in an aqueous environment be carried away by the point where the nitrogen is necessary, which makes it ineffective «,

In the dispersion materials according to the invention, nitrogen is present chemically bound, which makes any physical separation impossible and therefore ensures an advantage of this type of detergent will.

Also, it is advisable to only develop the microbial species too secure those responsible for the breakdown of hydrocarbons are. The detergent does not contain a phosphorus element as it is intended for use in a natural environment that does so Contains element in sufficient quantity. An increase in assimilable phosphorus would have the disadvantage of eutrophication (French word: eutrophisation) to favor the recipient environment.

The novel biodegradable compounds according to the invention, which are provided with detergent properties arise from

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the chemical bond between glutamic acid and a hydroxyl compound as defined below, and an alkylene oxide «

The hydroxyl compound is reacted with the alkylene oxide ^ and that The resulting oxyalkylate is treated with glutamic acid.

The glutamic acid used in this invention can open your or Iiaktam- shape may be used, which represents the pyroglutamic acid · The usable in the invention hydroxyl compound is a 1 _a 2-alkane diol having 10 to 30 carbon atoms, or the product from the partial acylation of an aliphatic polyol having from 2 to 10 carbon atoms with the following formula:

CH ₂ OH

CH ₂ CH
j or X — C — Y

CH ₂ OH I.

CH ₂ OH

in which J. is hydrogen, a grouping CH ₂ OH or an alkyl radical - preferably a linear one containing 1 to 6 carbon atoms, and Y can be H, CH ₂ OH or OH, the acylation with a fatty acid, preferably a linear, saturated or unsaturated fatty acid having 10 to 30 carbon atoms or with one of its derivatives of the carboxyl group, for example ester, acid anhydride or acid halide.

Partial acylation is understood to mean an acylation that relates to at least one alcohol group

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of the polyol "and leaves free at least one alcohol group (preferably a primary or secondary alcohol group), on which one can later add an alkylene oxide according to the process of the invention lets react.

The alkylene oxides which are part of the chemical compound according to the invention are alkylene monooxides with 2 "to 4 carbon atoms * Among _{those containing hydroxyl groups). Compounds y} which are part of the detergent compounds according to the invention can be mentioned:

The 1,2-diols, which originate from the action of the peracids on the olefins, and in particular the 1,2-diols, which are derived from the olefin fractions ^G ₁ 2 ~ ^G 20 ^a ^ '' ^{e3 / fcen} * Glyfcolmonostearat, Glykoimonooleate , G-lycerine monostearate, glycerine monooleate, G-lycerine laurate and, generally speaking, the monoesters of glycerine

£ om
and of natural fatty acids such as tallow, coconut oil, tall oil esters, soybean oil which are sold industrially, the monooleate of trimethylolpropane (TMP), monostearate of! C, MP _e , monolaurate before / TMP «and, generally speaking, the esters of Τ, Μ.Ρ And industrial fatty acids of natural origin derived from tallow, coconut oil, tallow ester and soybean oil, the monooleate of pentaerythritol, ionostearate of pentaerythritol, monolaurate of pentaerythritol and, in general, the monoesters of pentaerythritol and of industrial fatty acids of natural origin ,

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- 7 coconut oil, tall oil ester, soybean oil.

Among the alkylene oxides that can be used according to the invention, one can mention: ethylene oxide, propylene oxide, butylene oxide, butylene oxide is preferred for reasons of "biodegradation. The oxyalkylation reactions are carried out using an alkaline catalyst.

The number of reaction sites for the alkylene oxide is determined by the number of hydroxyl groups present that are capable of to react with him.

The proportion of the alkylene oxide as well as its type depends on the hydrophilic-lipophilic balance (EHL) that is obtained wants to achieve, for the 3PaIl of ethylene oxide, which is advantageous When used in accordance with the present invention, amounts of oxide will be between 20 and 80% by weight relative to the final compound use.

The reaction of the product from the oxyalkylation with glutamic acid or its pyroglutamic acid derivative is preferably obtained by the reaction of one mole of glutamic acid with each free Hydroxyl group either in the absence of a solvent or in an inert solvent such as an aromatic hydrocarbon, carried out, whose task is to entrain the water formed during the reaction: The reaction temperature is between 100 and 200 ° C., preferably between 120 and 150 ° C. The reaction can catalyze with an acid catalyst, such as paratoluene sulfonic acid, or you do not catalyze, The obtained Compound is an ester of pyroglutamic acid.

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If the glutamic acid has not esterified all of the hydroxyl groups, the reaction may be terminated by adding another acid, e.g. a fatty acid, this acid esterifies the remaining OH groups of the polyol, but the lactam ring of the Pyroglutamic acid ester is not changed.

The following examples explain the invention

Example 1:

137.2 g are passed into a 1 liter pressure cooker reaction vessel (or 0.71 OH equivalent) "Alfol 12" (linear primary alcohol, commercially available from Condea) and 1.4 g of liatrium methylate. After the air has been removed, he "

hitzt it then is added in small portions with good stirring, 110 ml of ethylene oxide added (volume in the liquid state at 20 C measured) to ^r 130 C, wherein the discharge is regulated by decreasing the internal overpressure "The experiment is 1 hour after the End of the introduction of the ethylene oxide. 232.6 g of oxyethyl alcohol are obtained. The hydroxyl number is 0.32 OH groups for 100 g. The degree of bound ethylene oxide is about 41 wt .- ^.

Example 2:

It is fed into a 250 ml glass flask with a magnetic Agitator, a cooling device and a device for

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Removal of the water produced by the reaction is provided, 100 g of the alcohol prepared according to Example 1, 47 g of glutamic acid and 35 ml of xylene. The mixture is heated with stirring in an inert gas envelope in an oil bath "at 200 0 for 9 hours, the environment has become homogeneous at the end of the reaction" 10 _and 5 ml of water are removed. After evaporation of the xylene, 133.4 g of an ester are obtained of pyroglutamic acid, the saponification index "is 0.22 ester groups for 100 g»

Example 5?

One works in the same way as in Example 1, starting from 183.1 g of monooleate of trimethylolpropane, which according to a known Procedure is prepared, 2 g of sodium methylate and 233 ml of ethylene oxide, at 120 C for 4 hours 30 minutes. One wins 383.9 g of an oxyäthylxerten product whose saponification index is 0.09 ester functions for 100 g and whose hydroxyl number 0.23 OH groups for 100 g. The level of bound ethylene oxide is approximately 52% by weight.

Example 4:

Esterifying 366 g of the alcohol prepared according to Example 3 with 127 g of glutamic acid in 140 ml of xylene at 200 ⁰ C for 21 hours in a .inerten gas envelope. 30.5 ml of water are obtained. The homogeneous solution obtained is evaporated; 461.3 g of the product are obtained. The saponification index is 0.22 ester

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groups for 100 g.

Example 5 s

If the procedure is as in Example 3, 415 ml of ethylene oxide are allowed to react with 381.3 g of glycerol monostearate (commercially available monostearin) in the presence of 3 »8 g of sodium ethylate. 739 g of product are obtained, the hydroxyl number of which is 0.40 OH groups / 100 g " ⁵ (one OH group is equal to 17 g).

■ Example 6i

Under the conditions of Example 4, 737 g of the alcohol obtained in Example 5 are esterified with 290.3 g of glutamic acid in 200 ml of xylene. After 4 hours 20 minutes if heating at 200 ⁰ C, during which one 69 ml of water was removed by Äzeotropie, is obtained 957 g of product.

Example 7:

Internally as in Example 3, you leave 357 ml of ethylene oxide react with 300 g of glycerol monooleate (commercially available monoolein) in the presence of 3 g of sodium methylate. 605 g are obtained of the product, the hydroxyl number of which is 0.35 OH groups / 100 g ".

Example 8:

By working as in Example 4, 600 g of des are esterified Product of Example 7 with glutamic acid in 200 ml of xylene. Huh

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6 hours at 200 ° C., 51 ml of water are removed and 751 g are obtained of the product.

Example 9:
Dispersion test with crude oil:

Mix the Koweit crude and the dispersant in a proportion 2 to 1 (in parts by weight). 2 ml of this mixture are introduced into 100 ml of sea water (approx. 35 g HaCl / l water). After stirring, this mixture is poured into 1 liter of sea water · Man., Stir again and leave to stand for 1 hour. the The water layer (which contains the emulsion water-oil dispersant) is then ■ from the oil layer floating on the surface

will be

separated. The two phases are extracted with chloroform and the amount of oil is dosed by photocolorimetry. If (X is the amount of emulsified oil and β is the amount of oil floating on the surface, the stability of the emulsion is given by the following relationships:.

S «

Product of the example S % 2 54.7 4th 73 . 6th 100 8th 74

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Example 10:

Cleaning test with sand (Taylor test):

In this test 100 ml of sand (300 Ms 500 p.) Is used, the is soaked in sea water, 2.5 g of Koweit crude oil and 1.5 ml of des Dispersant. -The effectiveness "is 100% if the whole Crude oil when rinsing the sand with 200 ml of sea water, which is added in two sections, is removed from the sand. As in Example 9, the crude oil remaining in the sand and the crude oil emulsified by the water are extracted with chloroform and dosed by photocolorimetry.

Product of the example Effectiveness % 2
4th
6th
8th "25.6
51.2
15.5
47

Example 11;

Test of the biodegradability of a dispersant:

A sufficient volume of river water is taken to make it a microbial vaccine, which is separated by centrifugation and which is used to inoculate 150 ml vials that are distilled Contain water and nutritious salts. - monopotassium phosphate, Disodium phosphate, magnesium sulfate etc ...) and to which one was known Adds amounts of a dispersant.

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By removing the seed ens (C _Q), and 18 days are metered total organic carbon in each Piole on days later (, Clq), said Fiolen are maintained under stirring at 22 ⁰ C '

Product of the example Degree of biological
Degradability $> 2
4th
6th
8th 61.5
87.1
78.5
82.7

Example 12 i

read the biodegradability of a mixture of gas oil and Dispersant:

The procedure is as in Example 11, but you add gas oil, water, dispersing agent and the hydrocarbons by extracting the contents of the tubes with carbon tetrachloride and infrared metering according to the APNOR T 90 203 standard thus track the biodegradability of the hydrocarbons as a function of time.

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3 product of the example Degree of mining $ 18 2 days 6 saga 12 saga 88.7 2 30.5 '52.3 98.2. 4 · 29.1 58.1 96.8 6th 29.5 57.3 97.3 8th 28.7 54.2

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Claims (8)

- 15 claims ('1> Process for the preparation of a surface-active, biologically degradable chemical compound, characterized a) that one reacts an alkylene oxide with a hydroxyl compound which is chosen from the following: - The 1,2-alkanediols with 10 to 30 carbon atoms per Molecule, - des. Products resulting from the partial esterification of a aliphatic polyol with 2 to 10 carbon atoms and the following formula arise CH OH CH ₂ OH J 'or X-C-Y CH ₂ OH CH ₂ OH in which X is hydrogen, a group CH OH or an alkyl radical with 1 to 6 carbon atoms and Y is Η, OH or CH is OH, with a fatty acid having 10 to 30 carbon atoms or a reactive derivative of this acid and b) that the oxyalkylate obtained in section (a) with glutamic acid or allows pyroglutamic acid to react. 609828/1019 2. The method according to claim 1, characterized in that the Hydroxyl compound is a 1 "2-alkanediol. 3 «The method according to claim 1, characterized in that the hydroxyl compound is the product of the partial esterification of glycol or glycerin. 4, "A method according to claim 1, characterized in _t that the hydroxyl compound is the product of the partial esterification of trimethylolpropane. 5. The method according to claim 1, characterized in that the hydroxyl compound is the product of the partial esterification of pentaerythritol. 6. The method according to any one of claims 1 to 5, characterized in that that the alkylene oxide is ethylene oxide and that one binds an amount of ethylene oxide which is 20 to 85% by weight of the final compound represents. 7. A compound obtained by the process according to any one of claims 1 to 6. 8. Use of a compound which is obtained by the process according to any one of claims 1 to 6 in order to obtain a hydrocarbon, to disperse a petroleum fraction or a fatty substance in water. 609828/1019