WO2005014491A1

WO2005014491A1 - Etheramines and their nitriles as biocide for water treatment

Info

Publication number: WO2005014491A1
Application number: PCT/EP2004/008189
Authority: WO
Inventors: Gordon Moir; Paul J. Bailey; Miriam De Faria Lemos; Dimas Carlos De Campos; Antonio Pedro De Oliveira Filho
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2003-08-05
Filing date: 2004-07-22
Publication date: 2005-02-17
Anticipated expiration: 2006-02-05
Also published as: GB0318312D0

Abstract

This invention relates to the use of a compound of the formula (1); wherein R1 is a linear or branched C6-C30 saturated or unsaturated hydrocarbyl group, R2 is H, CH3, CH2CH3 or (CH2)2CH3, n is 1, 2, 3, 4 or 5, m is 0, 1, 2, 3 or 4, and X is NH2 or CN in a biocidal composition.

Description

ETHERAMINES AND THEIR NITRILES AS BIOCIDE FOR WATER TREATMENT

FIELD OF THE INVENTION This invention is concerned with the control of oilfield biofouling in order to reduce or inhibit corrosion and the presence of sulfate-reducing bacteria, general aerobic bacteria (GAB), slime formers and Gallionella that may be present in storage tanks, flowlines and pipelines and petroleum production facilities.

BACKGROUND OF THE INVENTION

Such micro-organisms may cause serious problems in oilfield systems such as, but not limited to, corrosion of steel, plugging and mal-functioning of equipment and processes such as injection wells, storage tanks, flow lines, pipelines and petroleum production facilities and in general souring (biogenesis of H₂S) of the facilities. Souring increases the cost of oil production, accelerating corrosion rates and decreasing efficiency of secondary oil recovery due to plugging of the reservoir by sulphate reducing bacteria biomass and precipitated metal sulphides and presents serious ESHA consequences due to it's highly toxic nature.

Probably the most troublesome micro-organisms are sulphate reducing bacteria (SRB) due their involvement in souring phenomena, and their capacity to form biofilms, complex structure of cells attached on surfaces, that renders them very resistant to biocide action. SRB are a wide group of strict anaerobes which use hydrogen or simple organic acid or even hydrocarbons in petroleum as electron donors for sulphate reduction. Another anaerobic bacteria like methanogenic, fermentative bacteria, nitrate and iron-reducing bacteria are also found in petroleum reservoirs.

Hydrogen sulfide is frequently detected in oilfield brines as a consequence of the activities of sulfate-reducing bacteria (SRB). The presence of hydrogen sulfide can present a series of problems in oilfields due its odor, toxicity and corrosive nature. General aerobic bacteria (GAB) like Pseudomonads and Flavobacterium or slime formers are capable to produce dense biomasses on solid surfaces that harbour anaerobic groups like SRB. The iron bacteria, as Gallionella also initiates an ecological succession, creating an anaerobic environment that enables SRB to grow. In similar way, other micro-organisms like algae and diatoms can be found in these environments and can cause problems such as those detailed above.

The petroleum companies treat these problems in different physical or chemical ways but the most common method is by the injection of biocides either continuously or as a batch treatment.

The microbial treatment has been completed with good results, for example, products such as quaternary ammonium compounds, glutaraldehyde, isothiazolone derivatives, formaldehyde, acrolein, sodium hypochlorite, tetrakis- hydroxymethyl-phosphonium sulfate (THPS) or tetrakis-hydroxymethyl- phosphonium chloride (THPC) or combinations of any two or more have been use to control SRB. The success of these products depends on the killing efficiency of the product and the ability of the biocide to penetrate biofilms and act against the SRB, GAB and other oilfield bacteria.

We have discovered that etheramines, etherdiamines, ethertriamines, ether- tetramines and ethernitriles with a fatty chain substituent, optionally neutralized with an organic or inorganic acid in combination with alkylhydroxylethyldimethylammonium chloride and alkyldimethylbenzylammonium chloride are good biocides against sulfate-reducing bacteria (SRB) and other bacteria present in water in the petroleum industry.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a novel, environmentally friendly biocide and to its use as a bactericide to inhibit and control the growth of sulfate-reducing bacteria and other bacteria present in the waters used and processed in the petroleum industry.

More particularly, the invention relates to a biocide composition with use and application to improve the protection of facilities of petroleum production, storage tanks, pipe-lines and distillation columns in refineries against corrosion caused by sulfate-reducing bacteria.

The biocide composition of this invention is further characterized by a wide bactericidal spectrum, including but not limited to sulfate-reducing bacteria.

Object of this invention is a biocide composition, comprising a compound of the formula 1 R² R² R¹ - O - [C ¹ H]_n - [ rNH - [C ' H]J 1_m - X (1 )

wherein R¹ is a linear or branched C6-C30 saturated or unsaturated hydrocarbyl group, R² is H, CH₃, CH2CH3 or (CH₂)2CH₃, n is 1 , 2, 3, 4 or 5, m is 0, 1 , 2, 3 or 4, and

X is NH₂ or CN.

R¹ may be an alkyl, alkenyl or alkynyl group. In a preferred embodiment of the invention R¹ has from 6 to 24, particularly 8 to 20 and especially 10 to 18 carbon atoms.

This invention further relates to the use or the compounds of formula 1 in biocidal compositions.

This invention further relates to a method for treating a water system susceptible to infection by aquatic microorganisms in order to inhibit the growth of the latter, which method comprises adding to said water system at least one compound of formula 1.

This invention further relates to a method for treating a water system susceptible to corrosion provoked by aquatic microorganisms, which method comprises adding to said water system at least one compound of formula 1.

The compounds of formula 1 are preferably added in an amount from 1 to 2,000ppm, but particularly between 5 and 500 parts per million of the water to be treated.

The water system may contain industrial cooling or process water. The water may come from a power station, chemical plant, steel or paper mill or brewery. The water system may contain injection water for oil fields or produced water in oil flowlines and water handling and disposal systems.

The water system may also contain water selected from geothermal water and water in central heating systems, air conditioning systems, and for use in hydrostatic testing, swimming baths and as cooling water for ships and marine engines.

The biocide composition of this invention preferably may be composed of, as an active ingredient, at least one of the following compounds:

a) etheramines R2 R - O— f- CH ] -NH₂ (2)

wherein

R¹ is a linear or branched C₆-C₃o saturated or unsaturated group, such as an alkyl, alkenyl, or alkynyl group,

R² is H, CH₃, CH₂CH₃ or (CH₂)₂CH3, n is 1 , 2, 3, 4 or 5;

b) etherdiamines R² R³ Rⁱ-O- CH]-N-r- C^ NH₂ (3) H wherein R¹ is a linear or branched C₆-C₃₀ saturated or unsaturated group, such as an alkyl, alkenyl, or alkynyl group, R², R³ are H or CH₃, CH₂CH₃ or (CH₂)₂CH₃, n, o are 1 , 2, 3, 4 or 5;

c) ethertriamines

R² R³ R⁴ Rⁱ — O -r- CHj^N-f- C^-N-f ^•c^ -NH, (4) H H H ^P

wherein

R¹ is a linear or branched C₆-C₃₀ saturated or unsaturated group, such as an alkyl, alkenyl, or alkynyl group,

R², R³, R⁴ are H, CH₃, CH₂CH₃ or (CH₂)2CH₃, n, o, p are 1 , 2, 3, 4 or 5;

d) ethertetramines,

R² R¹ — O-h CH]— (5)

wherein

R², R³, R⁴, R⁶, are H, CH₃, CH₂CH₃ or (CH₂)2CH₃, n, o, p, q are 1 , 2, 3, 4 or 5. or salts therefrom with either acetic acid, acrylic acid, citric acid, nitric acid, phosphoric acid, carbonic acid, phosphorous acid, hydrochloric acid or sulfuric acid.

In the above-shown formulae 2 - 5, the terminal NH2 group may be replaced by CN. Such compounds are also within the scope of the invention.

The biocidal composition includes blends with one or more of the following: a quaternary ammonium compound and condensation reaction products of etheramines and formaldehyde, paraformaldehyde, glyoxal and, or glutaraldehyde. The mixing ratio may be from 1 :99 to 99:1 , preferably from 10:90 to 90:10, particularly from 25:75 to 75:25.

The biocide composition of this invention may comprise a quaternary ammonium compound, amine, or salt thereof. Suitable quaternary ammonium compounds include, but are not limited to, those having the formula: [R¹R²R³R⁴N]⁺ X- (6)

wherein R¹, R², R³, and R⁴ independently are linear, branched, cyclic or any combination thereof, saturated or unsaturated groups, and X is an anion. The sum of the number of carbon atoms in R¹, R², R³, and R⁴ broadly ranges from about 6 to about 30. R¹, R², R³, and R⁴ may be alkyl, alkenyl, alkynyl, cycloalkyl, aryl, or any combination of any of the foregoing. X may be chloride, carbonate, bicarbonate, nitrate, bromide, acetate, carboxylates, sulphate or methoxylated sulphate.

A preferred quaternary ammonium compound has the formula

[R¹(CH₃)₃N]⁺X- (7) wherein R¹ is a linear or branched C₆ -C-₂o saturated or unsaturated group, such as alkyl, alkenyl, or alkynyl group and X is defined as above. More preferably R¹ is a linear Cβ-Cis saturated or unsaturated group and X is chloride, carbonate, acetate, sulphate or metho-sulphate.

Another preferred quaternary ammonium compound has the formula

[R¹ R² (CH₃)₂ N]⁺X- (8)

wherein R¹ is a linear or branched C₆-C₂o saturated or unsaturated group or C₆-C-₂o substituted or unsubstituted aryl group, R² is a linear or branched C₁-C₂₀ saturated or unsaturated group or C6-C20 substituted or unsubstituted aryl group, and X is defined as above. We define as substituted any combination of, but not limited to, substitution with any one or any combination of the following substituents: Cι-C₄ alkyl. Preferably, R¹ and R² independently are linear or branched C₈-Cι₆ saturated or unsaturated groups. In a more preferred embodiment, R¹ and R² independently are linear or branched Cs -C₁2 saturated or unsaturated groups and X is chloride, carbonate, or acetate.

Another suitable quaternary ammonium compound has the formula

[R¹ R² (CH₃)₂ N]⁺X^' (9)

wherein R¹ is a substituted or unsubstituted benzyl group, R² is linear C₁₀ to C₂o saturated or unsaturated group, and X is defined as above. According to a preferred embodiment, R¹ is benzyl, R² is a linear C₁₂-C1.₈ saturated or unsaturated group, and X is chloride.

Another quaternary ammonium compound contemplated for use in the present invention has the formula

[R¹R²N(CH₃)(CH₂CH₂O)nH]⁺ X^' (10) wherein R¹ is a C₆-C₂o linear or branched, substituted or unsubstituted alkyl group or a C₆-C₂o substituted or unsubstituted aryl group, R² is a C1-C20 linear or branched, substituted or unsubstituted alkyl group or a C₆-C20 substituted or unsubstituted aryl group n is an integer from 1 to 5, and X is defined as above. Preferably, R¹ and R² are linear or branched C₈-Cι₀ substituted or unsubstituted groups and more preferably are decyl. X is preferably chloride.

Another suitable quaternary ammonium compound has the formula

[R R R³(CH₃)N]⁺X- (11 ) wherein R¹, R², and R³ independently are linear or branched C₆-C₂₂ saturated or unsaturated groups. More preferably R¹, R², and R² independently are linear or branched Cs-C-io saturated or unsaturated groups. X is preferably chloride.

A particularly preferred compound is a fattyhydroxylethyldimethyl ammonium chloride of the generic molecular formula

wherein R¹ is a C₆-C₂o linear or branched, substituted or unsubstituted alkyl group or a C₆ -C20 substituted or unsubstituted aryl group, R² is a Cι -C₂₀ linear or branched, substituted or unsubstituted alkyl group or a C₆ -C₂o substituted or unsubstituted aryl group n is an integer from 1 to 5, and X is defined as above. Preferably, R¹ and R² are linear or branched C₈ -C₁₀ substituted or unsubstituted groups and more preferably are decyl. X is preferably chloride.

Another particularly preferred compound is a fattydimethylbenzyl ammonium chloride of the generic molecular formula:

wherein R¹ is a C₆-C2o linear or branched, substituted or unsubstituted alkyl group or a C-6 -C20 substituted or unsubstituted aryl group, R² is a Ci -C-₂0 linear or branched, substituted or unsubstituted alkyl group or a C₆ -C2₀ substituted or unsubstituted aryl group, and X is defined as above. Preferably, R¹ and R² are linear or branched C₈ -C₁0 substituted or unsubstituted groups and more preferably are decyl. X is preferably chloride.

Preferably, the biocide composition comprises a mixture of quaternary ammonium compound and an etheramine or ethernitrile, neutralized with an organic or inorganic acid in an aqueous solution with a pH between 4 to 10.

More preferably, the biocide composition comprises a mixture of neutralized etheramine or ethernitrile, a quaternary ammonium compound, and a glycol in an aqueous solution.

The most preferable form the biocide composition of this invention comprises is a mixture of neutralized etheramine or ethernitrile and a benzalkonium chloride in an aqueous solution. This form of composition is biodegradable.

The biocide composition may be prepared with any amount of said active ingredient(s) therein. It is also possible to prepare from a concentrated solution which can be diluted in commercially available glycols, alcohols or water for the actual use. Preferably, the active ingredient(s) of said composition may be present in an amount of from 0.001 weight percent to 1 ,0 weight percent on the total weight of the biocide composition. In the following example all parts and percentages are by weight, and such example will not limit the present invention to such extent.

EXAMPLES

Microbiologic Methodology Sessile cultures: Sulphate reducing bacteria (SRB) used in these assays were isolated from water samples of oilfield industrial plant. The cultures are maintained into flasks with API Macae modified medium with iron cylinders coupons as a biofilm. For the assays, the SRB culture is inoculated in API Macae modified medium with iron coupons and incubated for 72 hours. The bacterial cells attach on the coupon surface forming a biofilm.

Kill Time Test: the contaminated iron cylinders are washed twice with sterilised distilled water and put in biocide water solution. Each concentration is tested in triplicate. The contact time is, in general, two hours. After this, the cylinders are washed again and put in 10 ml flasks containing API Macae modified medium, and incubated at 32°C for 21 days. The evaluation is done after 24 hours, 7, 14 and 21 days.

Bacteriostatic activity assay: the contaminated coupons are sonicated for two minutes, washed twice with destilated water, and directly put in 10 ml flasks with Macae medium with the desired concentration of the biocide. In each assay, A control without biocide is carried out

Example of formulation

The biocide composition of the present invention was prepared by mixing etheramine, monomethylglycol, acid, benzalkonium chloride (Preapagen^® HY, Clariant) and water. (All percentages are against the total weight of said composition). All formulations are presented below. Examples of formulations tested

EMA = Ethermonoamine iso - C-io 50 % neutralized with acetic acid,

HOE = Ethermonoamine iso -C₁₀,

HY = Alkyl dimethylethanolamine chloride 40 % in water,

MEG = Monoethylene glycol a) acetic acid, b) chloroacetic acid, c) nitric acid

Products tested without modification

Products Description EDA 2835 Etherdiamine salt neutralised with acetic acid, branched chain C-ι₃. EDA 2835 - 2L Etherdiamine salt neutralised with acetic acid; linear chain C₁₂.₁ . EDA 3135 Etherdiamine salt neutralised with acetic acid, branched chain C-ι₀. EMA Ethermonoamine partially neutralised; branched chain C₁₀. Genamin CC100 Coconut fatty acid amine

Examples 1 and 2

Several products amine based were evaluated in their biocide and bacteriostatic activity. In these assays a SRB culture isolated from Cabiύnas water sample (PB01) was grow for 72 hours attached on a iron cylinders coupons in order to form a biofilm. All the assays were performed with API Macae modified medium containing 3.0% of NaCI. The denotion „ + " means that there was some bacterial growth observed in the test and that the biocide was insuccessful at that test concentration. The denotion

means that there was no growth observed in the test and that the biocide was successful at that test concentration. The tests were performed in triplicate, and the results are given by e.g. (+++) and (++-).

Example 1 - Bacteriostatic activity

Formulation Concentration (ppm) 20 50 100 200 a EDA 2835 (+ + +) (+ + +) (+ + +) (+ + +) b EDA 2835 - 2L (+ + +) (+ + +) (+ + +) (+ + +) c EDA 3135 (+ + +) (+ + +) (+ + -) ( — ) d Flotigan EDA (+ + +) (+ - -) (- - -) (- - -) e 031/02-05* (+ + +) (+ + +) (+ + +) (+ - -) f Dodigen 1611 (+ + -) (^{+ +} -) (^{+ +} ") (" - -) g Glutaraldehyde (+ + +) (+ + +) (+ + +) ( — ) h THPS (+ + +) (^{+ +} ") (" - -) (- ^" -) i Control (+ + +)

*1 :1 :1 -A mix of EDA 3135, EDA 2835 and EMA. THPS - Tetrakis(hydroxymethyl)-phosphoniurr) sulfate, Dodigen 1611 - Dimethyl Alkylbenzylamonium Chloride,

Example 2 - Kill time test

Formulation Concentration (ppm)

500 1000 1500 a EDA 2835 (+ + +) (+ ⁺ ") (+ - -) b EDA 2835 -2L (+ + +) (+ - -) (+ + -) c EDA 3135 (---) (+--) (+--) d EMA (+--) ("--) (-"-) e 031/02-05* (+ + +) (+ - -) (+ + +) f Cocoamine (DC) (+ + -) (+ ^■-) (---) g Dodigen 1611 (+ + ^■) (⁺-^") ("-) h Glutaraldehyde (---) (--^") (---) i THPS (+ + +) (+--) (---) k Control (+ + +)

1:1:1 mix of EDA 3135, EDA 2835 and EMA, Dodigen 1611 -Dimethyl Alkylbenzylamonium Chloride, THPS -Tetrakis(hydroxymethyl)phosphonium sulfate, Cocoamine - Fatty amine of coconut,

EMA showed the better performance among the amine based products tested. Its performance was quite similar to the glutaraldehyde.

Examples 3 and 4

It was prepared several formulations contained the ethermonoamine Flotigan EDA, and the assays for evaluation their performance as biocides against SRB were carried out. The methodology was the same described above. Example 3 - Bacteriostatic activity

Formulation Concentration (ppm) 50 100 150 200 a Fongrabac THQ4 (+ + +) (+--) ( + --) (...) b 065/02-6 (+ + -) (---) ( -") (...) c 065/02-14 (+ + -) (---) ( ---) (+--) d 065/02-15 (+ + -) (+ + -) ( ---) (...) e 065/02-17 (+ + -) (⁺--) ( ---) (...) f Control (+ + +)

Example 4 - Kill Time Test

Formulation Concentration (ppm) 500 1000 1500 2000 a Fongrabac THQ4 (+ ^{+ +}) ( .._) (...) ( — ) b 065/02-6 (---) ( ---) (...) ( — ) c 065/02-14 (---) < + + -) (...) ( — ) d 065/02-15 (+ + -) ( ..-) (+--) ( — ) e 065/02-17 (---) ( ---) (...) ( — ) f Control (+ + +)

The formulations 065/02-6 and 17 showed the better performance in both bacteriostatic and bactericidal activity.

Example 5

In these assay the aim was the determination of the MIC values of formulations for a PB-01 SRB culture. The methodology was same described above for bacteriostatic activity. Example 5 - MIC determination

Formulation Concentration (ppm) 20 50 70 100 120 150 170 200 220 250 065/02 - 6 (+--) (+--) (-"-) (---) (---) (---) ("--) (-") ("--) (-"-) b 065/02 - 14 (+ + +) (+--) (⁺ + ⁺) (---) (---) (--") (+--) (--") (---) (--") c 065/02-15 (+' (...) ₍₊..) (+..) (...) (...) (...) (...) (...) (...)

T 065/02-17 (+ + +) (+--) (---) (---) .(---) (---) (---) (--") (---) ("--) e Control (+ + +)

In the conditions of the test, the MIC values of formulations against the PB-01 culture of SRB are the following:

Formulation MIC f 065/02-6 between 20 and 50 ppm g 065/02-14 100 ppm k 065/02-15 between 20 and 50 ppm i 065/02-17 between 50 and 70 ppm

Example 6 The following assays were performed with API Macae culture medium prepared with sea water. The products tested were the formulations 065/02-17 and 23. The aim was also to determine the MIC values in order to evaluate the effect of Praepagen HY in the formulation.

Example 06 - Bacteriostatic activity

Formulation Concentration (ppm)

065/02-17 (+ + +) (+ + +) (^{+ +} -) (+--) (+--) ("^• -)

065/02-23 (+ + +) (+ + +) (+ + -) (+ + -) (+ + -) (" -)

Control (+ + +) The MIC values are higher when the assay is performed with culture medium prepared with sea water. The susceptibility of SRB to formulation 23 is slightly lower than of formulation 17.

Example 7

In this assay were introduced two new formulations (006/03-24 and 25) and compared them with 065/02-17 and 23. These formulations were neutralised with nitric acid instead acetic acid.

Example 7 - Bacteriostatic activity

Formulation Concentration (pprr 1) 50 100 150 200 250 300 a 065/02-17 (+ + +) (+ + +) (...) (...) (...) (...) b 065/02-23 (+--) (...) (...) (...) (...) (...) c 065/02-24 (+ + +) (...) (...) (...) (...) (---) d 065/02-25 (+ + +) (...) (...) (...) (^"-) (...) e Control (+ + +)

There are no important differences between the formulations 23, 24 and 25.

Claims

Claims:

1. Use of a compound of the formula 1

R² R2 R1 - O - [C ¹ H]„ - [ rNH - [C IH]_n i]_m - X (1 )

O wherein R¹ is a linear or branched C₆-C₃o saturated or unsaturated hydrocarbyl group, R² is H, CH₃, CH₂CH₃ or (CH₂)2CH₃,0 n is 1 , 2, 3, 4 or 5, m is O, 1 , 2, 3 or 4, and X is NH₂ or CN in a biocidal composition.

2. A method for treating a water system susceptible to infection by aquatic microorganisms in order to inhibit the growth of the latter, which method comprises adding to said water system at least one compound of formula 1.

3. A method for treating a water system susceptible to corrosion provoked by aquatic microorganisms, which method comprises adding to said water system at least one compound of formula 1.

4. Use according to claim 1 , wherein fattyhydroxylethyldimethyl ammonium salt of the generic molecular formula

wherein R¹ is a C₆-C₂o linear or branched, substituted or unsubstituted alkyl group or a C₆ -C₂o substituted or unsubstituted aryl group, R² is a C₁ -C2₀ linear or branched, substituted or unsubstituted alkyl group or a CQ -C₂₀ substituted or unsubstituted aryl group, n is an integer from 1 to 5, and X is an anion such that the fattyhydroxylethyldimethyl ammonium salt is soluble is used as a further component.

5. Use according to claim 1 , wherein fattydimethylbenzyl ammonium chloride as of the generic molecular formula

wherein R is a C6-C2₀ linear or branched, substituted or unsubstituted alkyl group or a C₆ -C20 substituted or unsubstituted aryl group, R² is a C₁ -C2₀ linear or branched, substituted or unsubstituted alkyl group or a C₆ -C2₀ substituted or unsubstituted aryl group, and X is an anion such that the fattydimethylbenzyl ammonium salt is soluble is used as a further component.

6. Use according to claim 1 , wherein the compounds of formula 1 are added in an amount from 1 to 2,000 parts per million of the water to be treated.

7. Biocide composition, comprising a compound of the formula 1

R² R² R¹ - O - [CH]_n - [NH - [CH] J_m - X (1 )

wherein

R¹ is a linear or branched C₆-C₃₀ saturated or unsaturated hydrocarbyl group, R² is H, CH₃, CH2CH3 or (CH₂)2CH₃, n is 1, 2, 3, 4 or 5, m is 0, 1, 2, 3 or 4, and

XisNH₂orCN.