USE OF A COMPOSITION AND METHOD FOR REDUCING BACTERIAL SPORES IN PULP SUSPENSION

Abstract

The invention relates to use of a composition comprising a cationic surfactant, which comprises a primary or secondary ammonium head group and a linear unsubstituted C12-alkyl tail, for inducing germination of bacterial endospores in pulp suspension for making of paper, board or the like. The invention relates also to a method for quantitatively reducing bacterial endospores in pulp suspension for making of paper, board or the like. The method comprises obtaining of aqueous pulp suspension, and administering the said composition to the pulp suspension. The cationic surfactant is allowed to interact with bacterial endospores in the pulp suspension. Germination of endospores and destroying microorganisms is thus induced.

Claims

1. A use of a composition comprising a cationic surfactant, which comprises a primary or a secondary ammonium head group and a linear unsubstituted C12-alkyl tail, for inducing germination of bacterial endospores in pulp suspension for making of paper, board or the like.

2. The use according to claim 1, wherein the composition comprises at least 10 weight % of the cationic surfactant, an organic solvent, which comprises at least one OH group, and optionally water.

3. The use according to claim 1, wherein the cationic surfactant is n-dodecylamine or dodecylguanidine salt, being dodecylguanidine hydrochloride.

4. The use according to claim 1, wherein the composition comprises 10-60 weight-%, preferably 20-47 weight-%, more preferably 25-45 weight-%, of the cationic surfactant.

5. The use according to claim 1, wherein the composition comprises 10-90 weight-%, preferably 10-60 weight-%, more preferably 10-50 weight-%, even more preferably 20-47 weight-%, sometimes even more preferably 25-45 weight-%, of organic solvent.

6. The use according to claim 1, wherein the organic solvent is selected from glycols and alcohols, such as ethanol, isopropyl alcohol and dipropylene glycol.

7. The use according to claim 1, wherein the composition comprises biocidal agent, such as a water-soluble biocide.

8. The use according to claim 7, wherein the biocidal agent is a non-oxidizing biocide selected from group comprising glutaraldehyde, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1,3-diol, carbamates, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-dibromo-2,4-dicyano butane, bis(trichloromethyl)sulfone, 2-bromo-2-nitrostyrene, 4,5-dichloro-1,2-dithiol-3-one, 2-n-octyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, ortho-phthaldehyde, quaternary ammonium compounds, other guanidines than dodecylguanidine salts, biguanidines, pyrithiones, 3-iodopropynyl-N-butylcarbamate, phosphonium salts, dazomet, 2-(thiocyanomethylthio)benzothiazole, methylene bisthiocyanate and any combinations thereof.

9. The use according to claim 7, wherein the composition comprises 0.01-20 weight-%, preferably 1-20 weight-%, more preferably 5-15 weight-%, even more preferably 7-10 weight-%, of the biocidal agent.

10. A method for quantitatively reducing bacterial endospores in pulp suspension for making of paper, board or the like, comprising: obtaining aqueous pulp suspension, administering a composition comprising a cationic surfactant, which comprises a primary or a secondary ammonium head group and linear unsubstituted C12-alkyl tail to the pulp suspension, allowing the cationic surfactant o interact with bacterial endospores in the pulp suspension, and inducing germination of endospores and destroying microorganisms by using a biocidal agent, heat or by the cationic surfactant itself.

11. The method according to claim 10, wherein the cationic surfactant is n-dodecylamine or dodecylguanidine salt, such as dodecylguanidine hydrochloride.

12. The method according to claim 10, wherein administering the composition comprising cationic surfactant is to at least one of the process locations selected from a pulp and/or broke storage tower, a pulp thickener, a pulp and/or broke pulper.

13. The method according to claim 12, wherein administering the composition comprising cationic surfactant is in an amount that provides a negative delta spore value between inlet and outlet of the selected process location.

14. The method according to claim 10, wherein administering the composition comprising cationic surfactant is in an amount that provides a dosage of the cationic surfactant to the pulp suspension in the range of 1-1000 ppm, preferably 10-500 ppm, more preferably 50-200 ppm, calculated as active cationic surfactant.

15. The method according to claim 10, wherein administering is an oxidizing biocide to the pulp suspension.

16. The method according to claim 15, wherein the oxidizing biocide is administered to the pulp suspension in an amount of 1-30 ppm, preferably 5-20 ppm, more preferably 7-10 ppm, as total active chlorine or percarboxylic acid.

17. The method according to claim 10, further comprising adding a chelating agent, such as DTPA or EDTA, to the pulp suspension at the latest with the administration of the cationic surfactant.

18. The method according to claim 17, wherein adding a chelating agent, such as DTPA or EDTA, to the pulp suspension is in an amount of 1-100 ppm, preferably 10-50 ppm, more preferably 15-25 ppm, given as active agent.

Description

EXPERIMENTAL

[0041] Some embodiments of the invention are described more closely in the following non-limiting examples.

EXAMPLE 1

[0042] This on-site side-flow test was performed at an alkaline board machine, which produces 3-ply food packaging board, in order to test efficacy of Composition 1-1 according to the invention and comprising cationic surfactant against total aerobes and aerobic spores of broke tower (consistency 3.5%, pH 7.2, Oxidation Reduction Potential, ORP, +158 mV). Cationic surfactant was dosed (contact time 90 min, 180 rpm) as 150 ppm dodecylamine into broke sample, which after total aerobes and aerobic spore counts were quantitated (plate count agar, +45? C./+37? C., 2 days incubation) at an external laboratory. Prior to the bacterial spore determination, samples were pasteurized at +80? C. for 20 min. Results are shown in FIG. 1. The left hand column shows the broke reference sample with no added biocide, the right hand column the broke sample dosed with Composition 1-1.

[0043] FIG. 1 shows that the untreated broke (3.5% consistency, pH 7.2, ORP +158 mV) contained much aerobic bacteria, 14 000 000 cfu/ml, as well as aerobic spores, 300 cfu/ml. The use of Composition 1-1 according to the invention markedly decreased total aerobes from 14 000 000 cfu/ml to 200 cfu/ml and aerobic spores from 300 cfu/ml to 40 cfu/ml. Obtained results thus indicate that the Composition 1-1 can effectively hygienize broke with an economically feasible dosage. Eventually such broke hygienization treatment enables food packaging board mills to produce the highest hygiene board grades with maximum bacteria content of 250 cfu per gram of dry final board.

EXAMPLE 2

[0044] This on-site side-flow test was performed at an alkaline board machine, which produces 3-ply food packaging board, in order to test efficacy of Composition 1-2 according to the invention and comprising cationic surfactant against total aerobes and aerobic spores of incoming mechanical pulp (consistency 5.4%, pH 6.5, ORP ?190 mV). The cationic surfactant was dosed (+48? C., 75 min, 180 rpm) as 150 ppm dodecylamine into pulp sample. Total aerobes and aerobic spore counts were quantitated (plate count agar, +45? C./+37? C., 2 days incubation) at an external laboratory. Prior to the bacterial spore determination, samples were pasteurized at +80? C. for 20 min. Results are shown in FIG. 2. The left hand column shows the pulp reference sample with no added biocide, the right hand column the pulp sample dosed with Composition 1-2.

[0045] FIG. 2 shows that the untreated incoming pulp (5.4% consistency, pH 6.5, ORP ?190 mV) contained much aerobic bacteria, 1 000 000 cfu/ml, but no spores, <10 cfu/ml. Due to the dosing of Composition 1-2, total aerobes were effectively killed as the level decreased from 1 000 000 cfu/ml to 200 cfu/ml. Obtained results thus indicate that Composition 1-2 can effectively hygienize pulp despite the high fibre content (5.4% consistency) and low ORP (?190 mV) at economically feasible dosage rate. Eventually the hygienisation of pulp enables food packaging board mills to produce highest hygiene board grades where bacteria content is max 250 cfu per gram of dry final board.

EXAMPLE 3

[0046] This on-site side-flow test was performed at an alkaline board machine, which produces 3-ply food packaging board, in order to test efficacy of the method according to the invention against total aerobes and aerobic spores of broke tower (consistency 3.5%, pH 7.2, ORP +65 mV). The cationic surfactant, i.e. Composition 1-3, was dosed (75 min, 180 rpm) as 150 ppm dodecylamine into broke sample, and there after post-treated (30 min, 180 rpm) with sodium hypochlorite (as 10 ppm active chlorine) in order to improve killing effect against vegetative and germinated cells. Total aerobes and aerobic spore counts were quantitated (plate count agar, +45? C./+37? C., 2 days incubation) at an external laboratory. Prior to the bacterial spore determination, samples were pasteurized at +80? C. for 20 min. Results are shown in FIG. 3. The left hand column shows the broke reference sample with no added biocide, the middle column shows the broke sample dosed with Composition 1-3, and the right hand column the broke sample dosed with Composition 1-3 and with sodium hypochlorite.

[0047] FIG. 3 shows that the untreated broke (3.5% consistency, pH 7.2, ORP +65 mV) contained much aerobic bacteria, 37 000 000 cfu/ml, and some aerobic spores, 70 cfu/ml. The composition 1-3 markedly decreased level of total aerobes from 37 000 000 cfu/ml to 1 600 cfu/ml, and showed also sporicidal effect as the aerobic spore counts decreased from 70 cfu/ml to 30 cfu/ml. Bacteria and spore killing effect was further improved by introducing a sodium hypochlorite post-treatment, as 10 ppm active chlorine. The microbiological quality of the broke was drastically improved; total aerobes content decreased from 37 000 000 cfu/ml to 400 cfu/ml, and aerobic spore counts from 70 cfu/ml to 10 cfu/ml. Obtained results thus indicate that the method according to the invention provides an economically feasible solution for broke hygienisation, which eventually enables food packaging board mills to produce the highest hygiene board grades with maximum bacteria content of 250 cfu per gram of dry final board.

EXAMPLE 4

Reference

[0048] This laboratory test was performed in order to test killing effect of sodium hypochlorite against total aerobes and aerobic spores in broke sample (consistency 1.0%, pH 7.8, ORP +146 mV) taken from an alkaline board machine, which produces 3-ply food packaging board. Total aerobes and aerobic spore counts were quantitated by using plate count agar (+45? C./+37? C., 2 days incubation). Prior to the bacterial spore determination, samples were pasteurized at +80? C. for 20 min. Results are shown in FIG. 4. The left hand column shows the broke reference sample with no added biocide with 1 day contact time, the right hand column the broke sample dosed with sodium hypochlorite with 1 day contact time.

[0049] FIG. 4 shows that the untreated broke (1.0% consistency, pH 7.8, ORP +146 mV) contained much aerobic bacteria, 650 000 cfu/ml, and some aerobic spores, 70 cfu/ml. Sodium hypochlorite treatment, as 10 ppm active chlorine, showed only weak killing effect, as total aerobes level remained at high level, 390 000 cfu/ml, despite the chlorine treatment. Similarly, the sodium hypochlorite treatment, as 10 ppm active chlorine, was ineffective against mature spores, as aerobic spore content remained at close to initial level of 60 cfu/ml. Obtained results thus indicate that sodium hypochlorite, as 10 ppm active chlorine, alone may not be used to effectively hygienize broke.

EXAMPLE 5

[0050] This test was performed in a pilot paper machine producing 1-ply paper. Aim of the test was to verify efficacy of the invention to provide a low quantity of aerobic bacteria and aerobic bacterial spores in dry paper end-product. Composition 1-5 comprising 40 weight-% of dodecylamine, 40 weight-% of dipropylene glycol and 20 weight-% of water was used according to the invention. It was dosed as 100, 150 or 300 mg/l into pulp suspension with 2.25% consistency. The pulp suspension was then mixed 120 rpm for 30 min at +40? C. The pulp suspension was made from a batch of authentic, spore-contaminated folding-box board with average spore content of 7000 cfu/gram of dry board. All pulp suspensions in the pilot paper machine were also post-treated (5 min, 120 rpm) with glutaraldehyde (dose: 50 ppm as active agent) in order to maintain control of vegetative bacterial cells in the pilot machine. Total aerobic bacteria (without pasteurization) and aerobic spores (with pasteurization step at +82? C. for 10 min) were quantified from the dry paper end product according to the ISO 8784-1 standard for microbiological examination of paper and board.

[0051] FIG. 5 as well as Table 1 show results from microbiological examination of the dry paper samples that were produced in the pilot paper machine with different dosages of Composition 1-5 in the pulp slurry.

TABLE-US-00001 TABLE 1 Results of example 5. Total aerobic Aerobic bacteria spores (cfu/g) (cfu/g) Reference paper, without 1 973 1 423 added composition to the pulp Paper 1 523 414 Dosage: 100 mg/l composition 1-5 Paper 2 108 20 Dosage: 150 mg/l composition 1-5 Paper 3 70 18 Dosage: 300 mg/l composition 1-5

[0052] FIG. 5 and table 1 show that the reference paper contained high quantity of aerobic bacteria (1973 cfu/g) and aerobic bacterial spores (1423 cfu/g). This indicates that the contaminated raw material with high initial endospore content caused subsequent contamination of the produced paper. The treatment with the glutaraldehyde biocide was not alone capable to lower spore contamination in the produced paper.

[0053] Use of Composition 1-5 according to invention markedly decreased level of endospores in final paper at every tested dosage level. The method according to the invention showed sporicidal effect lowering the spore counts 1423 cfu/g (reference) to 414 cfu/g (with 100 mg/l treatment) or to 20 cfu/g (with 150 mg/l treatment) or to 18 cfu/g (with 300 mg/l treatment). Similarly, the total aerobic bacteria counts from the dry paper were significantly lower. Obtained results thus indicate that the invention provides a feasible solution for paper end-product hygienisation at a reasonable dosage level, which eventually enables food-packaging paper and board mills to produce the highest hygiene grades with maximum bacteria content of 250 cfu per gram of dry final paper or board.

EXAMPLE 6

[0054] This laboratory test was performed to compare biocidal efficacy of three test products, namely a conventional biocide Composition R comprising glutaraldehyde (reference), and Compositions 1-6 and 2-6, which comprised a cationic surfactant comprising a primary ammonium head group and linear unsubstituted C12-alkyl tail, and a cationic surfactant comprising a secondary ammonium head group and linear unsubstituted C12-alkyl tail. Composition R comprised 50 weight-% of glutaraldehyde. Composition 1-6 comprised 40 weight-% of dodecylamine, 40 weight-% of dipropyleneglycol and 20 weight-% of water. Composition 2-6 comprised 35 weight-% of dodecylguanidine hydrochloride and 65 weight-% of dipropyleneglycol.

[0055] Products were tested against Total aerobic bacteria and Aerobic spores in authentic process water taken from a paper machine producing food-packaging board. At the moment of sampling from process, the authentic process water contained high amounts of Total aerobic bacteria, >100 000 cfu/ml, but very few Aerobic spores, <100 cfu/ml. In order to be better capable to evaluate product efficacies against Aerobic spores, the process water was spiked with additional spores, targeting for Aerobic spore level of ca. 100.000 cfu/ml. This spore solution for spiking was prepared as follows: Authentic spore-forming bacteria that were isolated from a paper making process were pre-grown for 2 days at +37? C. in modified nutrient broth, after which the mature spores were harvested, and washed by using centrifugation and cold water.

[0056] At the start of the test, the spore spiked process water was divided into eight individual samples. Two samples were treated with Composition 1-6, two with Composition 2-6 and two with a conventional Composition R. Compositions were dosed in such amount that the active amount of active agent was the same (90 mg/l) in each sample. In addition two samples were stored as such and used as 0-reference samples, without any added biocide. Samples were stored at 45? C., 180 rpm mixing, for 50 minutes, followed by quantification of Total aerobic bacteria (non-pasteurized samples) and Aerobic spores (plate count agar, +37? C., 2 days incubation). Prior to the aerobic spore determination, samples were pasteurized at +82? C. for 10 min. Results are shown as average values of two parallel samples in FIG. 6 and Table 2.

TABLE-US-00002 TABLE 2 Results of example 6. Total aerobic Aerobic spores bacteria (cfu/ml) (cfu/ml) 0-reference 379 000 92 000 (no added biocides) Composition 1-6 5 050 2 500 (90 mg/l Dodecylamine) Composition 2-6 3 300 760 (90 mg/l Dodecylguanidine hydrochloride) Composition R, reference 655 000 115 000 (90 mg/l Glutaraldehyde)

[0057] Results in FIG. 6 and Table 2 for 0-reference sample clearly show that the process water, after spiked with spores, contained a large amount of Total aerobic bacteria, 379 000 cfu/ml, and Aerobic spores, 92 000 cfu/ml. Composition 1-6 effectively decreased Total aerobic bacteria level from 379 000 cfu/ml to 5050 cfu/ml and Aerobic spore level from 92 000 cfu/ml to 2500 cfu/ml. Composition 2-6 effectively decreased Total aerobic bacteria level from 379 000 cfu/ml to 3300 cfu/ml and Aerobic spore level from 92 000 cfu/ml to 760 cfu/ml. It is seen that both Compositions 1-6 and 2-6 were surprisingly effective in decreasing Total aerobic bacteria as well as Aerobic spores. On the contrary, reference Composition R was non-effective against Total bacteria and Aerobic spores. Obtained results thus indicate that the use of two tested Compositions 1-6 and 2-6 according to the invention, containing dodecylamine or dodecylguanidine hydrochloride as active agent, can be effective for hygienization of paper making process streams with high total bacteria and aerobic spore content.

EXAMPLE 7

[0058] This laboratory test was performed to evaluate efficacy of a Composition 1-7 according to the invention and comprising a cationic surfactant comprising a secondary ammonium head group and linear unsubstituted C12-alkyl tail, against Total aerobic bacteria and Aerobic spores in authentic process water taken from a paper machine producing food packaging board. Composition comprised 35 weight-% of dodecylguanidine hydrochloride and 65 weight-% dipropyleneglycol.

[0059] At the start, the process water was divided into four individual samples; two were treated with Composition 1-7 and two samples were stored as such and used as 0-reference (process water without added biocides). Samples were stored at 45? C., 180 rpm mixing, for 30 minutes, followed by quantification of Total aerobic bacteria (non-pasteurized samples) and Aerobic spores (plate count agar, +37? C., 2 days incubation). Prior to the aerobic spore determination, samples were pasteurized at +82? C. for 10 min. Results of two parallel samples are shown as average values in FIG. 7 and Table 3.

TABLE-US-00003 TABLE 3 Results of example 7. Total aerobic Aerobic spores bacteria (cfu/ml) (cfu/ml) 0-reference 1 162 500 70 (no added biocides) Composition 1-7 <100 25 (90 mg/l Dodecylguanidine hydrochloride)

[0060] Results in FIG. 7 and Table 3 show that the process water as such contained a large amount of Total aerobic bacteria, 1 162 500 cfu/ml, and some Aerobic spores, 70 cfu/ml. Composition 1-7, at active agent dosage of 90 mg/l Dodecylguanidine hydrochloride, showed excellent hygienisation effect of the process water. Total aerobic bacteria level dropped from 1 162 500 cfu/ml to <100 cfu/ml, which is below practical detection limit, and the level of Aerobic spores decreased from 70 cfu/ml to 20 cfu/ml. Obtained results thus indicate that the Composition 1-7, with dodecylguanidine hydrochloride as the active agent, may effectively be used to hygienize paper making process streams containing aerobic bacteria and bacterial spores.

[0061] Even if the invention was described with reference to what at present seems to be the most practical and preferred embodiments, it is appreciated that the invention shall not be limited to the embodiments described above, but the invention is intended to cover also different modifications and equivalent technical solutions within the scope of the enclosed claims.