DE1492418A1 - Process for combating biological contamination in paper mills - Google Patents

Description

NALCO CHEMICAL COMPANY, 6216 West 66th Place, Chicago, Illinois, V.St.A.

Methods for controlling biological contamination in paper mills

The invention relates to a method for the prevention and elimination of biological problems in the plants of the Ganestoff production and recovery and the wet end of papermaking operations and it relates in particular to biological control in papermaking processes, whereby the biological active compound methylene-bis-thioeyanate used will.

It has recently been found that methylene-bie-thiocyanate has a high level of biological activity. Remarkably small amounts, for example a few ropes per

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Million or less of this compound, have the ability to kill a wide variety of microorganisms commonly found in industries such as paper mills, Cooling towers, secondary extraction systems and the like occur to combat.

The production of this extraordinarily effective connection is expensive and if it takes a long time Periods of time for the treatment of systems contaminated with special genera are used There is a risk that their effectiveness will decrease. The persistence of the organisms becomes remarkable when methylene bis-thiocyanate is used to treat paper mill equipment will. The use of this compound in papermaking is unfavorable because of this reduction in the Activity limited after repeated use and also because of the high cost.

After observing numerous paper mills, it has been found that a variety of biological situations or Forms appear · Un better understand these forms and to better explain the inventive ideas, it seems expedient to compare the actual paper mill process with the first treatment stages of cellulose fibers in two separate processes.

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to divide up activities or steps. These steps or stages are referred to as (I) the Ganastoff • manufacturing and recovery process and (II) the nasal area process. AIb basis of the explanations and of the later descriptions it should be noted that the stock production and recovery system in a typical mill, facilities such as the Dutch or the hydropaper kneading machine, the storage chute (stock most likely), the cone pulp mill or refiner and specialized waste and separation systems. The wet end system contains equipment such as machine chests, Whole tool box, bird screen, head container and the roller or Fourdrinier machine8 proper.

When examining these two general types of systems with regard to microbiological contamination, it has been found that these can be divided into categories containing the following groups of microorganisms: a. predominantly all bacterial; b «predominantly all yeasts;

c. predominantly bacterial in the Gansetoff production and Ruokgewinming system, predominantly yeasts in the Nasal system;

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d. mainly yeast in the Ganzetoff production and Recovery system, mainly bacterial im Wet end system;

e. mixed bacterial and yeast in both the stock · manufacturing and recovery system and in the wet end system.

These categories indicate that large numbers of microorganisms thrive in these water-laden, nutrient-rich systems. Examples of bacteria and yeasts which grow in the two systems mentioned are: Pseudomonas aeruglnosa "Aerobacter cloacae _a Stre ptococcus faecaliji" Bacillus pumilus ,, Micrococcus {jiypgenee. Bacillus sub tilis, Aeroba ^ t ^ r, aerofienes « Bacillua mycoides, De aul fpvibrio desulfuricans» Clostridia and yeasts such as Trichoderma , Tor ula and Ilonilia.

The invention proposes a treatment process in which methylene bis-thiocyanate is combined with fungicidally active Halogen-substituted phenols and their alkali metal salts and other germicides, as further described below. According to the invention it is also planned to use these substances in conjunction with dispersants to create a complete program for the treatment of the two systems mentioned above

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create. It is therefore the object of the invention to provide a selective system for combating microorganisms in To create paper and pulp mills in which methylene-bis-thiocyanate along with a large number of biologically active chemicals are used.

Another object of the invention is to provide an effective ' To create means to optimize the activity of methylene bisthiocyanate as a microbiocide. Other tasks will be apparent from the following description.

To the biological effectiveness of the methylene-bis-thiocyanate To clarify, the results of biological tests carried out in the laboratory are given below Evaluations of this compound against bacteria and felts are shown. The test method used corresponds the conditions found in many industrial systems where microbiological problems exist. The test method is described in detail below.

Test method

The culture used consisted of 24 g of dextrose and 1 g of Basaminbact (Anheuser Busch), which was added to 1 1 of Chicago tap water . The whole thing was in the autoclave

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Sterilized at 15 pounds pressure for 15 minutes. The final pH of the medium was 6.8 £ 0.1. An equivalent amount of an 18 to 24 hour culture broth of A. aerogenes or spore suspension of A. was mixed with 200 ml of the culture medium immediately before the start of the experiments in order to obtain an inoculated culture medium with one million organisms per ml of medium. This inoculated culture medium was added to each of a series of fermentation tubes with a cap which contained the appropriate concentration of the test preparation so that a final volume of test preparation and culture medium of 20 ml was present in each tube. For this reason, the maximum volume of the introduced preparation had to be 0.5 ml per tube in order to avoid a chemical disruption of the solution. Many active solvent carriers are somewhat effective in their own right, and satisfactory comparative tests require that only small amounts of these solvents be incorporated into the culture medium. The preparation and the inoculated medium were gently mixed. Two control experiments were also performed, one in which the oculated medium was omitted and one in which the chemical preparation was omitted. While mixing, the A. aerogenes gas inhibition test was done by inverting the tubes around the gas detection vials

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to fill. The test tubes for the inhibition of growth inhibition of A. niger were shaken. Areas of inhibition for A. aerogenes were determined by the presence or absence of gas formation in the gas vials after 48 hours of incubation at 36.67 ° G (98 ° F). The A. niger test tubes were incubated for 5 days at 30 ° C (86 ° P) and the inhibitory effect was determined at the end of this period by observing the growth in the tubes.

In addition to the 48-hour inhibition test for Asergillus_Aerobacter ae ropenes and the 5-hour inhibition test for Aspergilj.ua niger , the effectiveness of the test preparations was also determined with regard to the 1 and 24-hour kill ranges. As stated in the above test method, an equivalent amount of an 18 to 24-hour nutrient broth culture of A. aerogenes or a spore suspension of A. niger was mixed with 200 ml of culture medium to produce an inoculated culture medium iaii; Obtain 1 million organisms per ml of culture medium. This inoculated culture medium was then placed in RöTirchen, which contained appropriate amounts of the test preparation, taking care that the final volume of the test chemical and the culture medium in each tube was 20 ml. The maximum amount of

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Introduced test preparation wax 0.5 ml per tube to avoid interference from the tea solvent. The inoculated medium and test preparation were then mixed gently, for example by shaking the tubes when testing A. niger fungal growth inhibition and to fill the gas detection vials when testing A. aerogenes inhibition. were turned. After 1 and 24 hours of contact with the test preparations, parts of the liquid were diluted 1000-fold in order to stop the effect of the preparation. The diluted samples were then placed in sterile culture tubes, brewed for 48-72 hours at 30 ° C, and then examined for growth. The results of these tests then show the 1 and 24 hour kill ranges.

Using the test method described above, the following results of the activity of methylene bisthiocyanate were found.

A._aerogenee (bacteria) TZVi ⁺ A. niger (mushrooms) T / M *

1 hour 24 hours 48 hours 1 ötd. 24 hours 5 days Killing Killing inhibition Killing Killing inhibition management

x ==== 332 = sa333 = cs = 33 = 3sa3S = 3a S3333S33asasasa33S33 = as =: ss3a

100 1.0-2.5 0.5-1.0 100 1.0-2.5 0.5-1 * 0

· »■ Parts per million methylene bis-thiocyanate.

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As already mentioned, the invention provides daa methylene-bis-thiocyanate to be used together with other microbiocidal agents to produce specific biological problems in papermaking « ▼ experienced combat. Other bactericidal agents which can be used in conjunction with ethylene bis thiocyanate are generically listed in Table I. cited.

Table I. Group A

halogenated ketones (0.01 - 1) group B

halogenated esters (0.01 - 1) group 0

3,5-dimethyltetrahydro-1,3 · 5 * 2H-thiadiaain-2-thione

(0.01 - 1)

Group D

Halogen or halogen-donating compounds (0.05-5) group E i

halogenated alkenes (0.01-1) group F.

Amines and polyamines (0.05-5) Group G

quaternary ammonium salts (0.05 - 5)

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Group H.

Thiocarbamates (0.01-1) Group I.

Aldehydes (0.01 - 1)
Group J

Sulfones (0.01 - 1)

Enter the numbers listed in brackets in Table I. typical effective amounts of these compounds in pounds per ton based on the weight of the finished product Papers made by a conventional paper mill process at.

The biologically active halogenated ketones, the group A in Table I are _t fall into the IIS Patents 3,021,256 and 3,024,159 and in Belgian Patent Specification No. 63? 748. Examples of such compounds are the halogenated acetones and their alkali metal bisulfite addition products, and so ketones such as: 2-chloroacetylfuran, 4-chlorobutanone-2, 3-chlorobutanone-2, 1-chlorohexanone-2, of-chloro-βf-phenyl * Acetophenone, it§ -Trichloracetophenon, Benssylacetondichlorid, CK-Chlor-df-phenylacetone, öf-Chlorpropiophenon, fi «Chlorpropiophenon, p-Chlorophenacylchlorid, p-Bromophenacylbromid,

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Ni'-chlorophenacyl chloride, d, "-chloroacetophenone * * 2,4-dichloro" acetophenone, meta ^ bromophenacyl chloride, p-hydrochlorophenacyl chloride.

Examples of shark ο gene st em that fall into group B, correspond to the formula:

f:
(R ₁ ) JO -CO- (R ₂ ) H

where R ^ is a halogen, hydrogen _r lower AXk? 1 ode :? lower halogenierfces Alkjl leg may "If Ii ^ a M" · is kylreat, he should no longer sweckiaäßigeriireiss u '.. s jvohlenatoffatome 6 _r tind preferably not Nohr aC.s; have 3 Xeiistoffatoine Thus "olclie lower äxl ^ / lfs. ^ ii li Äthyl _t Px'opyl, Isopropyl _? Butyl _t Isobutylg ns «-

Butyl _t tertiary butyl, aryl _r isoamyl and halogenated derivatives of these radicals. B'erner must at least one of the R ^ a halogen or a halogenated alkyl radical, such as an eroraid, chloride or the like. or an Alk with such a halogen. R "is an alkoxy niederere _f lower hydroxyalkoxy or lower Alkylpolyäther. Again, is very desirable _? that the number of hydrocarbons present in the radicals or in each repeating polyether unit is less than 6, and preferably 3 or less, so

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the term "lower", regardless of whether it relates to alkyl, alkoxy, hydroxy, alkoxy, halogenated alkyl or alkyl polyether radicals, stands for a substituted or unsubstituted hydrocarbon radical, which preferably has 1 to 6 carbon atoms, in particular preferably 1 to 5 carbon atoms _t "are most advantageous lower hydrocarbon residues that either 2 or 3 carbon atoms have * the carbon atoms have, of course, not necessarily arranged in a linear chain" and the radicals can also branched hydrocarbon radical containing that of the main or go out primary chain.

It has been found that the most useful water-soluble ·! organic haloesterallcohole the following general Have formula:

Il i- * j

(P _M ) -, C - Ο «0 f.GHpCCaJROyGEoO- / B.

where E ^ is a radical of the type mentioned above, R, either Is hydrogen or lower alkyl radicals, χ is one integer from 0 to 1 and y is an integer from 1 to ii is. In general, y will be 1 if χ is the same is. It eei repeats that in the case where R, a Is a hydrocarbon radical, regardless of whether an alkyl

9 O 9 8 U 9/1 3 7 3

13 y. U924ί8

group, a substituted alkyl group or a self repeating alkyl ether group, it should be less than Have carbon atoms, as already mentioned above.

As more preferred over halogenesfcers, those have been found proven that gokeim with the following general formula · » can be drawn:

H (R ₁ ) JC-C-O (R ^) -H

wherein R _{1 is} one of the radicals listed above, R _{11 is} ext. Radical from the group CH ₂ GH ₂ O, OH ₂ OHOHCH ₂ O and (GJhu <JH ₂ 0, where ζ can be an integer from 2 to 8,

Typical compounds of the composition mentioned are:

1 ~ bromoacetoxyethanol ~ 2,1-broraacetoxyethanol ~ 2 1-bromoacetoxypropanol ~ 5 1-chloroacetoxypropanol-3 1-chloroacetoxy-2-methylethanol-2 I-chloroacetoxyethanol-II-Qhl.oracetoxypropanol ^ .i-bromo-i ^ chloroacetoxyhexanol -e i-bromo-i-chloroacetoxyethanol-2 3-chloro-e _f

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1.1 ~ dibromoacetoxyethanol ~ 2 2,2-I) bromopropionoxybutanetriol "1 2,3 ~ dibromopropionoxyethanol ~ 2 2 "» Di chloro-2-bromoacet oxyethanol-1 1,1,1-tribromoacetoxyethanol-i 1-iodoacetoxyethanol ~ 1 i-'Pluoroacetoxyethanol-i

0
CH ₀ BrO - 0 «£ -CH CH _{o o} -f 0, -, - H

0
CH ₂ BrG - 0 -4-CH ₂ CH ₂ O - ~> / p ₆ H

Reaction product of polyvinyl alcohol and Broine reaction product of glucose and bromoacetic acid * bromoacetosypentaerythritol ~ 1

I, CH ₂ BrO - 0 «f-CEoCHoO - ^ ₂ H

Another group more biologically active halogenated "! *. Stars, which fall into group B, have the following structural formula:

R ₁ 0

rr ι.

C-C-O

ι ι

H ₁ R ₁

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Typical connections of this type are:

yerbindun ^ :. Name and ^ structure formeJL

N ~ lauryl bromoacetate

BrCH ^ -

II 1, j-dibromoisopropyl acetate

OH-C-O = CH

³ \

III methyl-2 _t 3 ~ ic: b.loropropionate

/ CH ₂ ClCH ₂ CL- CO- CH ^

IV I ^

CH _x C-0-OH

V methyl trichloroacetate

0 Cl _x C- ^ C- = OCH ₂

. . ". ,,. Λ ^ —U-— ..lliTfa I Il ' III 1 11 ■■ ι, ι'

VI methyl dichloroacetate

0
Cl ₂ CHC - 0 - CH,

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Connection urine and structural formula

VII methyl-2 * 3 - dibromopropiict O - O - GH,

VIII

IX

wywTSTT ^ cgc-;

XI

XII EthyI-2 _t 3 ~ dibromopropion & t

/ BrCH ₂ GHBrG ~ * 0 - ~ GH ^ CH

Ethyl 2-bromopropionate 0

- 0 ~

GH ₅ OH ₂ CH ₂ GHBrGH ₂ C

GH ₂ GH,

Methyl-2,

CH, 0 GH ₂ BrC - G - 0

Br

GH

XIII O ^ chloroplienylohloroacetate

0 GHCl - C - 0 -

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el

XIV diethyl bromomalonate

C.
Br

0-0-0H ₂ CH ₅ ) ₂

Diethyl IS-dibromosuccinate 0

X \ n methyl 3-bromopropionate

XVII ethyl 3-bromopropionate

• ■ ■ /

BrCHgCH ₂ C - OCHgCH,

XVIII methyl ~? -Bromo-n-butyrate

/ ■
CH ₅ GH ₂ CHBrG - 0 - O H ₃

Group D includes the known halogens, in particular
Chlorine and the halogen-releasing compounds, for example sodium chlorite and sodium and calcium hypochlorite The halogenated alkenes of group E are due to the known microbiocide 1, ^ - bis-bromoacetoacybutene. represent.

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Group F in Table I includes a variety of primary, secondary and tertiary monoamines and Polyamines. Likewise, group G includes a number of quaternary ammonium salts which are germicidal Have an effect.

Typical amines and quaternary ammonium salts are in

the article "Relative Toxicity of Biostatic Agents ^ m

Suggested for Use in the Pulp and Paper Industry - 1963 Reviews "by J. H, Conkey and J. A. Carlson Tappi, Volume 46, May 1963, listed.

Typical compounds are the fatty amines, for example N-Oc-fcyi-N-decylamine, the mixed fat-substituted triamines, diamines, such as N-oocotrimethylenediamine and octyldecyldi- · methylammonium chloride. Reference is also made to the publication Fungicides and Their Action by James G. Hörsfall, 194-5, as a general basis for typical amines "vegetable quaternary ammonium salts". Here amines are described on pages 131-133 and quaternary ammonium compounds on pages 136-139.

Group H in Table I relates to the use of compounds such as sodium dimethyldithiocarbamate and dinatriunicyandithioimidocarbamate.

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Group t in Table I suggests the biologically active Aldehydes »especially formaldehyde and its known Isomers and acrolein. It also includes the higher ones Aldehyde τ »! © JlöiBt & ldehyde.

Group J is characterized by the use of the compound bis-trichioraethyl sulfone. Further biologically active sulfones are described in U.S. Patents 3,075,692, 3 W 4-55, 3,136 68? _t 3,136,519 and 3,140,226.

Can be as stated above "the stock steilungs = · and Rückgewinnuiigssysteme and the wet end system containing a variety of microbiological contamination gen _t zwectonäBiEörwelae in five categories eingetoilt" I / o the NasspartioSystem and the whole fabric manufacturing and Rückgewinnuhgssystem contaminated with mainly all bacteria " According to the invention, one part of the system is treated with ethylene bis-thiocyanate and the other part with at least one of the germicidal agents listed in Table I. Where yeasts predominate in both systems ^ one part of the system is treated with methylene-bis-thiocyanate and the other part with a fungicidal halogenated phenol.

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Where the pulp manufacturing and recovery system If it is predominantly contaminated with bacteria, and yeast thrives in the wet end, the former system will too Methylene bis-thiocyanate and the latter system treated with a halogenated phenol. If the impurities occur in the reverse form, i. H. if that Yeast pulp production and recovery system and the nasal system contains bacteria, the former system is made with a halogenated phenol and the latter treated with methylene bis-thiocyanate.

Where mixed bacterial and yeast contamination occurs in both systems, methylene bis-thiocyanate and a germ named in Table I are used alternately. treated with killing agents.

To illustrate typical bacterial conditions described above, the following are bacterial analyzes different ranges given in typical paper mill systems:

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WET PARTY SYSTEM

BACTERIA

MUSHROOMS

1 - amount of organisms per 3 rams of the sample

Aerobic Flavo-
bacte Mu-
coide aero-
bac- do- Piuk forming I i mel Qex en “80,000 - - Monilia
I. j
I.
I. mm Sacc] Not spore forming - - 30,000 - B.Mega
therium I.
Other B.Subi species iTrichof Torula 9,000 - 5,000 Sample place
In the mill - - 1,000 • - sewage «. 100 5 ₅ 2OO, OOö - 300 Si ^ rimir- ¹
Leveling
oütte
(Leveling
chest) - 100,000 12, QOQ 100,000 = ■ _ 760,000 300 ** «
CD-
fs) Primer- ¹
machinery
bucket 8,000 600 210,000 - M. / orrat in ²
Machinery-
bucket - • - 10,000 - 950,000 300 m sealed
pit
(Semi fit) 20,000 6,000 50,000 - - 3,000,000 - 10,000 m Primary ²
Headers 10,000 30,000 200,000 - 1, OC - Trough ²

2 - amount of organisms per ml of the sample

and RECOVERY SYSTEM

bacterium

Pile «

aerobic - MlI Aero-i Pseu finch B.Me end Other
species Schim
mel To- B. efen sample Spurs
Non-spore forming image nu— bac- do- gathe B. Sttb- Tri- ru- Aeo- Saoona ⁹ * υπ «χη
J - Wed! ViI m Flavo- coiae ter monas rium tilis cho- Yes ni- ro «y- aer now ie bac- - the MA lia oea teriuij * - - 40,000 - - Secondary Ma - - 1,020,000 - - - machine chute - 1,000 - - - 3 Minien- ² 10,000 - - - - water - « 80,000 30th 400,000 - - Committee 700,000 100 8,800,000 - - - tank. - V. black fabric ■ - fen exempted. - - - - ■ - Goose fabric _s - 3,000 - 500 10,000 (Hiffler Stf ) - unbleached Goose fabric au 1 - - mm - Vac.Verdich- - - 2,000 - 500 13,000 (Seeker St ² ) - - - - - Knot- ^ - - - - 5,000 finger ² Uazixstoff f. - Back d. - - 20,000 - • Bl. (Vat ρ - - 320,000 - • - Backliner) * - - - - - - Flat sieve * - - 300,000 200 - 5O ₉ OOO - 200 - 1,000 - »
i . S.
NJ Casserole - 5,700,000 200 200 Vat) so ²

Orfanipmen per gram of sample;

? - amount of organisms per ml of the sample

-23- Ηί92Α18

In order to carry out ^ the above provisions, Samples from different areas of the paper mills enjoyed and examined to the nature and extent the biological contamination, as such investigations are required to identify the specific Categorize states in the IQhIe su. These determinations form part of the operations of the present invention.

To determine the total number, pseudomonae, flavobacteria and mucous bacteria, typical samples can conveniently be extracted on a Tripton glucose agar extract · To determine the extent of the spore-forming bacteria, the same medium can be used, but the sample is heated to 80 ° C must become. In the case of coliform bacteria and yeast becomes eosin-methylene-blue or potato dextrose agar for the provisions used. When SuIfat-Debilitating Bacteria or clostridia can be present using a specialty medium such as a sulfate-attenuating and anaerobic one Medium can be used. For algae and iron bacteria it is desirable to subject the sample to careful microscopic examination.

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These media are only given as examples and other known laboratory media can also be potted in. For a more detailed explanation of standard biological analyzes and media, see "The Difco Manual", 9th edition, Detroit, Michigan, 1963

After determining the type of biological contamination in the various parts of the plant, then nut an appropriate and appropriate treatment for the eu-solving task can be chosen.

If both in the wet end system and in the stock manufacturing and recovery system the contamination caused by bacteria is methylene bis-thiocyanate used together with a germicidal product, the active ingredient 2,5 ~ dimethyltetrahydro-1,3,5-2H-thiodiazine ~ 2-thione contains.

If the main contamination in both systems is yeast, treatment with one is appropriate Combination of pentachlorophenol and methylene bisthiocyanate. In the case of bacterial contamination in the Gaoz fabric manuf ellungs- and recovery system and mainly yeast in the Hasspartiesystem will treat accordingly with methylene bis-thiocyanate or pentachlorophenol

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carried out. BaI umtakahrten faxhaltnia becomes «nob dia ethylene-bia-thiooyanate biv. Pentachlorophenol . Treatment can be reversed.

A mixed bacterial and yeast occurrence in the two systems is effectively treated alternately with methylene bios-thiocyanate with bromoacetoxypropanoi or 2,5-dimethyltetrahydro-1,3,5-2H-thiadiazine-2-thione.

Another object of the invention is to provide the various treatment methods described above to combine with a dispersant that enhances the penetration and effectiveness of the described and Methylene bis-thiocyanate containing biological Means greatly improved. Suitable and typical compounds of this type are nonylphenols with 3-10 Hol ethylene oxides are implemented, in particular the nine-mole addition product. The fatty alcohols, such as lauryl alcohol, are also reacted with 3-10 moles of ethylene oxide and the various sulfonated lignins and codified lignins are useful for this. All of these products are excellent dispersants and have the additional advantage that they are only low foaming agents. That is important because excessive foaming is undesirable in paper mills. Of course, other dis-

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ftitfUraltt ·! «Mi IttaBitt ·! "El" he

mlextter find eloh la

ι Ton John V floOutcheon, 1963

Table II lists typical compounds which can be used in the combined treatment of ifethylene-bis-thioeyanate according to the invention .

Table II

QeBisch of ethyl ethers of the mono-,

Oi- and tripropylene glycol 23%

Pentachlorophenol 16 %

80 % active trichlorophenol 10%

Stoddard solvent (petroleum

deetillate of hydrocarbons

with 8 to 12 carbon atoms) 3 %

Non-ionic ethereal aliphatic polyoxyethylene surfactant that is 85 % active ingredients
contains 3%

Soft water 32 %

Potassium hydroxide (45 % in water) 13 %

100 %

BAD ORJGiNAL

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Verb * fK ^ T xg ΐ Sodium carbonate 27 Sodium chloride 20 Tetrasodium anhydrous pyrophosphate 2 Sodium as the 2,4,5-trichlorophenola 14 Sodium salt of pentachlorophenol 27

partially oxidized starch 5

Sodium hydroxide 2

Water 3

100 %

3,5-dimethyltetrahydro-1,31512H-thiadiaain-
2-thion 25 % Sodium hydroxide 25 % Isopropanol Q ⁰ L 2-mercaptobenthiaol c ot
• / · * Sodium lignosulfonate O fO Gluconic acid (50% in water) O £ ^ soft water 28%

100%

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Propylene glycol Broae acetic acid Toluenesulfonelure Polyalkylenated aliphatic base

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Claims (8)

1. Procedure for prevention and monitoring of biological Problems in the Genzatoff production and recovery systems as well as rabbit batch systems in paper production using τοη methylene-bis-thiocyanate, characterized in that the contaminated systems are substituted with a combination of methylene bis-thiocyanate and fungicidally active halogen Phenols and their alkali metal salts and / or other germicidal bactericidal agents are treated. 2. The method according to claim 1, characterized in that after determining the biological contamination divided into categories in the presence of: a) predominantly bacteria only part of the system with Methylene-bis-thiocyanate and the other part of the plant with at least one bactericidal compound, such as halogenated ketones, halogenated esters, 3,5-dimethyltetrahydro-1,3,5,2H-thiadiazine ~ 2-thione, halogen or Halogen-releasing compounds, halogenated alkenes, Amines or polyamines, quaternary ammonium salts, thiocarbamates, aldehydes or sulfones 9098A9 / 1373 H92418 b) predominantly all yeasts only a part of 4er Hethylene-bls-thlocyanat and the other part of the same with a fungicidally active halogenated «! fhenol or an alkali metal eelζ of the same c) predominantly bacteria in the pulp production and recovery plant and mainly yeast in the wet end, the former with ttethylene-bis-thiocyanate and the latter with a fungicidal balanced phenol or an alkali metal salt thereof d) mainly yeast in the Ganzetoff production and Recovery system and predominantly bacteria in the wet end, the former with a fungicidal halogenated phenol or an alkali metal as the same and the latter with methylene bis-thiocyanate e) mixed occurrence of bacteria and yeast in the raw material production and recovery plant and in the wet end alternately with methylene-bis-thiocyanate and at least one of those mentioned under a) bactericidal compounds is treated. 3. The method according to claim 1 and 2, characterized in that the bactericidal agent is 2,5-Dieethyltetrahydro-1,3,5,2H thiodiazine-2-thione is used. 909849/1373 U92A18 - 51 - 4. The method according to claims 1 and 3 t, characterized in that that there · 2, $ - Diaethylhjdz <o-1,9t5t2H-thiodiatin together with a sulfonated lignin as a dispersant. 5. The method according to claim 1 and 2, characterized in that bromoacetoxypropanol is used as the bactericidal agent will. 6. The method according to claim 1 and 2, characterized in that the fungicidal agent or pentachlorophenol an alkali metal salt thereof is used. 7. The method according to claim 1, characterized in that 2,5-diaetbyltetrahydro-1,3 «5t2H-thladlazine-2-thione is used as a bactericidal agent. 8. The method according to claim 7%, characterized in that the 315-Diaethjltetrahydro-1.3 _t 5-2H-thiadiazine-2-thione is used together with a sulfonated lignin dispersant. 9098 A 9/1373