CS215102B2 - Mixture for cleaning the river and sea water - Google Patents

Description

(54) Mixture for river and sea water purification

BACKGROUND OF THE INVENTION The present invention relates to a mixture for purification of river and sea water in a microbiological manner from diesel, petroleum products and derivatives thereof containing phosphorus and slow-release nitrogen in a form assimilated by aqueous microorganisms. The invention therefore relates to substances which are useful for promoting the dispersal of said pollutants, while at the same time providing nutrients which are an essential component necessary for the growth of naturally occurring and / or added microorganisms capable of oxidizing hydrocarbons and crude oil products.

Italian patent No. 981 945 describes and protects a process for the preparation and use of poorly water-soluble salt-based compositions which, by paraffinic treatment, become lipophilic and float on water, the latter containing nitrogen and phosphorus in the form of assimilated by aquatic microorganisms capable of metabolizing the hydrocarbonaceous material.

In the description of the invention to U.S. Pat. U.S. Patent No. 203,137 discloses and protects the addition of such mixtures containing poorly water-soluble salts, in particular paraffinated, hofecuate and ammonium phosphates, to lipophilic floating compounds, which compounds are capable of floating on their own or processed by paraffinization into such form, They also float on water, which compounds contain slow-release nitrogen, which can be assimilated by the microorganisms, at a P-h N / / naphtha ratio which is most favorable for biodegradation.

Compounds which are capable of fulfilling this purpose belong to the group of chemicals known as urea aldehyde derivatives.

It has also been found and observed that biodegradation, which is promoted by these compounds, can be further accelerated by the use of non-ionic dispersants.

These compounds exhibit a synergistic effect with respect to the action of the nutrients, thereby improving the distribution of the nutrients as such in the oil phase, which nutrients are contained in the above-mentioned mixtures.

According to the present invention, it has been found, and is the essence of the present invention, that lecithin, a phosphatide ester found in many natural sources, which may be of animal or vegetable origin, can effectively replace both the phosphorous source and the dispersing agent in the of the aforementioned mixtures.

In practice, it has been verified in the experiments of the present invention that lecithin is consumed by microorganisms which are capable of oxidizing hydrocarbons and which are commonly found in seawater, and thus constitute a source of phosphorus.

In addition, the present inventors have found that lecithin is an excellent emulsifying agent resulting from the presence of hydrophilic and lipophilic functional groups, and due to these emulsifying capabilities it can replace all or part of the capillary-active agents in the compositions mentioned above.

In addition, it has been found, and this constitutes another essential feature of the present invention, that in addition to the aldehyde-urea condensation products mentioned above, compounds belonging to a group of chemicals known as hydantoins and amides can advantageously be used as nitrogen sources, these substances can be easily assimilated by microorganisms capable of oxidizing hydrocarbons.

The nature of the mixture for the purification of river and sea water of naphtha, petroleum products and derivatives thereof containing phosphorus and slow-release nitrogen in a form assimilated by aquatic microorganisms according to the invention consists in that it contains lecithin and compounds belonging to the group The chemical compounds comprising hydantoins and / or the oxamide of the general formula h ₂ n-c-g-nh ₂ , oo preferably contain the compounds according to the invention in addition to the already mentioned components also compounds belonging to:

R 1 —CH — NHCOOH ₂ ,

Wherein R is

R is C 2 -C 6 alkyl, and

R ₁ represents an NH ₂ -CO-NH- or -OH group.

Also preferably, the mixture contains, in addition to locithine and compounds belonging to the group of chemicals including hydantoins and / or oxamide, phosphatides such as dihexadecanoylphosphotidylethanolamine of the general formula

CH ₂ OOC (CH ₂ ) ₁₄ —CH ₃

CH ₃ (CH ₂ ) ₄ —COO — CHO

I II

CH ₂ —O — P — O — CH ₂ —CH ₂ —NH ₃ ®

AND

Sloučeniny and compounds belonging to the group of chemicals including allophonates, polyamines of the general formula

NH ₂ - [(CH ₂ ) ,, - NH (CH ₂ ] _n .] _N. -NH ₂₎ in which n, n ', n "is from 1: to

4, furthermore the acyl racemates of the general formula

R-C-NH-CO-NH _2,

II o

in which it means

R is an alkyl radical of 1 to 7 carbon atoms with the hydantoic acid esters of the general formula

H ₂ N-CO-NH-CH ₂ -COOR in which R is an alkyl radical of 2 to 6 carbon atoms and allantoic acids of the general formula (NH ₂ -CO-NH) ₂ -CH-COOR in which R is an alkyl radical a C 2 -C 6 radical and also preferably comprises a mixture of the present invention in addition to the above-mentioned lecithin and a compound belonging to the group consisting of hydantoins and / or oxamide also phosphatides of the above formula and mixtures of compounds belonging to the group compounds including allophanates, polyamines of the above formula, acylroproteins of the above formula and esters of hydantoic acid and allantoic acid with compounds belonging to the group of urea aldehyde derivatives of the above formula.

Advantages of the composition of the present invention include the considerably increased rate of biodegradation of hydrocarbons when hydantoins and amides are used simultaneously with lecithin as the nitrogen source.

The compositions of the present invention are readily applicable in practical use since they do not require any special apparatus, and it is possible to adapt the first aid means for contamination, hydrocarbons, to these teachings.

The substances used in carrying out the purification according to the invention can be easily stored for an unlimited period of time, they do not belong to the group of toxic substances, and can also be easily transported to the place of use and easily spread to contaminated sites. Last but not least, these substances allow the removal of oil, petroleum products and derivatives thereof from fresh and sea water in a relatively short time.

An important advantage of the composition according to the invention is that substances which are of a natural nature and do not disturb the ecological balance are used to accelerate the natural process of biological degradation of the pollutants.

In fact, while the nutritional effect of the racemic aldehyde derivatives is derived from chemical hydrolysis, the nutritional effect of hydantoins and amides results from enzymatic hydrolysis that is caused by microorganisms themselves that are capable of oxidizing hydrocarbons.

Because the chemical hydrolysis of urea derivatives depends on physicochemical factors of water, especially temperature and pH, environmental situations can occur in which urea is released either in excess or inadequate due to the nutritional requirements of microorganisms capable of oxidizing hydrocarbons and in the first case the biodegradation is slowed down and in the second case the urea is imperfectly used, which is economically unfavorable.

There are no drawbacks in the prior art with the use of the hydantoin and amide chemicals of the present invention, since the nitrogen contained therein is released and consumed directly by the microorganisms themselves as needed.

The advantages of the composition of the present invention and other operating conditions used to apply the composition of the present invention will be set forth in detail in the following examples, which are incorporated herein by way of illustration only and are not intended to be limiting.

In addition, it has also been found in the context of the present invention that this constitutes a further advantageous feature of the present invention that it can be used both as a phosphorous source and as a phosphatide dispersant both of a synthetic and natural nature occurring in many sources, whether animal or vegetable.

Preferably, nitrogen sources that are assimilable by microorganisms that are capable of oxidizing hydrocarbons may be used, in addition to the compounds listed above which belong to the chemical family. known as hydantoins and amides, as already mentioned compounds belonging to the group of chemicals known as allophanates, polyamines, acylureas and allantoic acid esters.

Also, the nutritional effect of the above compounds is related as such to enzymatic hydrolysis by microorganisms themselves, which are capable of oxidizing hydrocarbons.

Moreover, it has been found that it is possible to achieve a significant increase in the rate of biodegradation of hydrocarbons when, in addition to the hydantoins and amides mentioned above, allophanates, polyamines, acylureas and hydantoic acid and allantoic acid esters are used together with phosphatides. both synthetic and natural.

The advantages of these blends are the same as that. this has already been mentioned above.

As mentioned above, the invention will be explained by means of examples of practice, which are included herein for the purpose of illustrating the process in more detail without restricting the substance in any way.

A 250 milliliter ground-necked Erlenmayer flask was used to fill 100 milliliters of non-sterilized seawater and 100 milligrams of crude oil obtained as a sample of the raw material mined in the vicinity of the Iraqi city of Basra.

(a) 5 milligrams of lecithin from soya and 5 milligrams of urea;

(b) 0,84 milligrams of potassium hydrogen phosphate K2HPO4 and 5 milligrams of urea,

(c) 5 milligrams of urea; and

(d) control sample without addition.

The individual vessels were incubated at 25 ° C using rotary stirring [100 rpm, eccentricity 5 centimeters). At time O · and then. every fifth day, the remainder of the feedstock is determined by extraction with carbon tetrachloride (CCl4), as described above.

The results obtained are shown in the graph of FIG. 1, where the ordinate indicates the residual raw material content, expressed as a percentage, and the abscissa indicates time in days.

Example 2

According to this embodiment, Erlen215102 250 milliliters mayer vessels having a ground neck are used and each contains 100 milliliters of unsterilized seawater and 100 milligrams of oil sample obtained in the vicinity of the Iraqi city of Basra, each vessel being filled with:

(a) 5 milligrams of soya lecithin and 6,5 milligrams of oxamide;

(b) 5 milligrams of lecithin and 13 milligrams of D-L-5-phenyihydantoin;

(c) 5 milligrams of lecithin from soybean and 10 milligrams of the isovaleric acid and urea condensation product obtained by the procedure of Example 3;

d) 5 milligrams of lecithin from soybean and 15 milligrams of the 3-phenylpropionic acid aldehyde condensation product and urea obtained under the same conditions used for the isovaleric acid aldehyde, see Example 3 below,

(e) control sample without addition.

The flasks are incubated and the residual hydrocarbon content determined by extraction as described above.

The results obtained are shown in Table I.

.Table I

Nutritional mixture 7

Incubation time (days)

19 25

and) 63,99+ 60.47 42.26 36.62 (b) 67.23 61.65 47.81 38.28 C) 63.74 54.43 44.91 40.06 (d) 59.78 54.85 47.79 43.17 E) 69.12 67.55 66.79 65.92

+ · Residual diesel in%

Example 3

According to this embodiment, 250-ml ground-necked Erlenmayer vessels containing 100 milliliters of unsterilized seawater and 100 milligrams of a sample of crude oil mined near Basra, Iraq, are each filled with:

a) 5 milligrams of lecithin from soybean, 5 milligrams of emulsifying agent, which in this embodiment is 2,2'-hydroxydiethyloleyl amide ·

CH ₂ CH ₂ OH

AND

CH ₃ - (CH ₂ ) _{7 -} CH = CH - (CH ₂ ) ₆ - C - CC) ONH ₂

CH ₂ CH ₂ OH and 10 milligrams of the · isovaleric acid-urea aldehyde condensation product obtained as follows: to 20 ml of an aqueous 25% solution of urea add 1 ml of glacial acetic acid and 2 ml of aldehyde. The mixture was allowed to stand and stirred at ambient temperature for three hours. The precipitate thus obtained is collected on a paper filter, washed with water and dried using a vacuum oven heated to 40 ° C, while drying for 24 hours.

(b) the same mixture as in (a), but without the use of an emulsifying agent,

(c) control sample without addition.

The results are shown in the graph of FIG. 2, in which the ordinate indicates the residual raw material content in percent and the abscissa indicates the time in days.

Example 4

In this embodiment, 250 milliliters Erlenmayer ground-necked vessels are used, each containing 100 milliliters of non-sterilized seawater and 100 milliliters of oil mined near Basra, Iraq, and each vessel is filled with:

(a) 5 · milligrams of soya lecithin and 5 · milligrams of urea;

(b) 5 milligrams of dihexadecanoylphosphatidylph ethanolamine and 5 milligrams of urea;

(c) 0,84 · milligrams of potassium hydrogen phosphate ΗΡ2ΗΡ04 and 5 milligrams of urea,

(d) 5 milligrams of urea;

(e) control sample without addition.

The vessels were incubated at 25 ° C with rotary stirring (100 rpm, eccentricity 5 centimeters).

At time point 0 and every fifth day thereafter, the residual feedstock content is determined by extraction with carbon tetrachloride CCI / 4 as above.

The results are shown. The graph in Fig. 3 shows the residual content of raw material in percent on the ordinate axis and the time in days on the abscissa axis.

Example. 5

In this exemplary embodiment, 250-ml Erlenmayer flasks having a ground neck are used, each filled with 100 ml of unsterilized sea water and 100 milligrams of crude oil mined near Basro, Iraq, to which the following vessels are added:

a) see example 2,

b) see example 2,

c) see example 2,

d) see example 2,

(e) 5 milligrams of lecithin from soya and 10 milligrams of ethylallophanate;

(f) .5 тШ§гатй leciihine from soya and 8 mdl · grams of spermidine, gj 5 milligrams of soya lecithin and 12 milligrams of phenylacetylurea,

(h) 5 milligrams of soya lecithin and 12 milligrams of butylhydantoinate, ij 5 milligrams of soya lecithin and 8 milligrams of butylallantoinate.

Said flasks are incubated, the residual hydrocarbon material (petroleum feedstock) being determined by extraction, as described above.

The results obtained are shown. in the following table II.

Table II

Nutritional Incubation Time (Days) Mixture 7 12 19 25

and) 83.99 + 60.47 42.26 36.62 (b) 67.23 61.65 47.81 38.28 C) 63.74 54.43 44.91 40.06 (d) 59.78 54.85 47.79 43.17 E) 66.12 59.77 46,00 36.12 F) 67.24 60.44 47.32 39.39 G) 65.66 56.11 45.28 37.21 (h) 61.88 56.19 47.29 39.18 and) 60.03 54.28 45.14 37.13

+ residual diesel in%. As can be seen from the results, the values obtained in Example 2 of Table I were fully confirmed, see mixtures a), b), c), d).

Claims (1)

OBJECT OF THE INVENTION 1. A mixture for the purification of river and sea water of diesel, petroleum products and derivatives thereof containing. phosphorus and slow-release nitrogen in a form assimilated by aquatic microorganisms, characterized in that it contains lecithin and compounds belonging to the group of chemicals including hydantoins and / or oxamide of the general formula H2N — C — C — NH2, O 0 preferably contains, in addition to the aforementioned components, compounds belonging to the group consisting of urea aldehyde derivatives of the general formula R ₁ —CH — NHCONH2, AND Wherein R is R is C 2 -C 6 alkyl, and R 1 represents an NH 2 -CO-NH- or -OH group, also preferably containing a mixture of lecithin and compounds belonging to the group of chemicals including hydantoins and / or oxamide also phosphatides such as dihexadecanoylphosphatidylethanolamine of the formula СН ₂ ООС (СН ₂ ) 1 ₄ —CH ₃ СНз (СН2) ₄ —СОО — СН O CH ₂ —O — P — O — CH ₂ —CH ₂ —NH ₃ ® And compounds belonging to the group of chemicals including allophanates, polyamines of the general formula NH ₂ - [(CH ₂ ) _n -NH (CH ₂ ) _n d _n ^ -NH ₂ in which n, n 'and n is a number from 1 to 4, acylureas of the general formula R-C-NH-CO-NH _2, Wherein R is alkyl having 1 to 7 carbon atoms, and hydantoic acid esters of formula H ₂ N - CO - NH - CH _{2 -} COOR, (NH _{2 -} CO - NH) _{2 -} CH - COOR, in which R is an alkyl radical of 2 to 6 carbon atoms, and also preferably contains a mixture in addition to the aforementioned lecithin and compounds belonging to the group of chemicals including hydantoins and / or oxamide still phosphatides of the above formula and mixtures of compounds belonging to the group of chemicals including allophonates, polyamines of the above formula, acylureas of the above formula and esters of hydantoinic acid and acids allantoin, with compounds belonging to the group of chemicals including urea aldehyde derivatives of the above formula. wherein R is C 2 -C 6 alkyl, and allantoic acid of formula