CA1239070A - Agents for defoaming and deaerating aqueous systems and the use thereof - Google Patents
Agents for defoaming and deaerating aqueous systems and the use thereofInfo
- Publication number
- CA1239070A CA1239070A CA000458161A CA458161A CA1239070A CA 1239070 A CA1239070 A CA 1239070A CA 000458161 A CA000458161 A CA 000458161A CA 458161 A CA458161 A CA 458161A CA 1239070 A CA1239070 A CA 1239070A
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- Prior art keywords
- aqueous systems
- defoaming
- agents according
- deaerating
- agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Paper (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
AGENTS FOR DEFOAMING AND DEAERATING AQUEOUS SYSTEMS AND THE
USE THEREOF
ABSTRACT OF THE INVENTION
Agents for defoaming and deaerating aqueous systems based on dispersions containing C14-C26 alcohols, per se known emul-sifiers and fatty acid esters of polyhydric alcohols, having at least 4 hydroxyl groups,the number of carbon atoms in the fatty acid or acids being 14 or higher. The inventive mixture of fatty alcohols and fatty acid esters has a marked synergistic action in defoaming and deaeraating aqueous systems. Partial fatty acid esters have proved particularly advantageous as fatty acid esters. The weight ratio of the alcohols to the esters is 2:1 to 10:1 and preferably 3.5:1 to 4.5:1. The average particle size of the dispersed, water-insoluble substances is 1 to 6 and preferably 2 to 3 µm. The agents according to the invention are universally usable and are suitable e.g. for deaerating and defoaming aqueous systems in the paints, pulp, paper, foods and drilling industries, as well as for deaerating and defoaming transport water in the processing of sugar beet and potatoes, or waste water and sewage.
USE THEREOF
ABSTRACT OF THE INVENTION
Agents for defoaming and deaerating aqueous systems based on dispersions containing C14-C26 alcohols, per se known emul-sifiers and fatty acid esters of polyhydric alcohols, having at least 4 hydroxyl groups,the number of carbon atoms in the fatty acid or acids being 14 or higher. The inventive mixture of fatty alcohols and fatty acid esters has a marked synergistic action in defoaming and deaeraating aqueous systems. Partial fatty acid esters have proved particularly advantageous as fatty acid esters. The weight ratio of the alcohols to the esters is 2:1 to 10:1 and preferably 3.5:1 to 4.5:1. The average particle size of the dispersed, water-insoluble substances is 1 to 6 and preferably 2 to 3 µm. The agents according to the invention are universally usable and are suitable e.g. for deaerating and defoaming aqueous systems in the paints, pulp, paper, foods and drilling industries, as well as for deaerating and defoaming transport water in the processing of sugar beet and potatoes, or waste water and sewage.
Description
BACKGROUND OF I~VE~TIO~
The present invention relates to agents for 5 deforming and decorating aqueous systems based on aqueous dispersions, which contain conventional deforming and decorating alcohols, specific fatty acid esters of polyhydric alcohols and conventional emulsifiers.
In industrial processes performed in aqueous media, the latter frequently have high air contents and/or disturbing foams frequently occur, thereby impairing the performance of the process and the quality of the products obtained. Thus, a number of processes and agents for 15 decorating and deforming aqueous systems have already been proposed. Therefore, the literature and particularly the patent literature dealing with this subject is very comprehensive. As this literature is well known to the expert, it will be sufficient at this point to refer in 20 exemplified manner to the summary description given in German patent 2,157,033.
German patent 2,157,033 proposes aqueous emulsions (or more correctly dispersions) for deforming aqueous 25 systems containing conventional deforming C12 to C22-alkanols and/or C12 to C22-fatty acid esters of dihydric or trihydric alcohols, as well as up to OWE based on the weight of the non-aqueous components, of paraffin oils and/or C12 to C22-fatty acids as foam removers, as well as 30 per so known additives of surfactants of an anionic, cat ionic or non ionic type as emulsifiers. According to the teaching of this patent specification, these per so known emulsions are relatively universally usable, provided that the average particle size of the emulsified, water-insoluble 35 substances is 4 to em The decorating and deforming agents according to German patent 2,157,033 are widely used in practice, but have proved to be ineffective in drilling muds.
Apart from the deforming compounds referred to in German patent 2,157,033, pentaerythritol fatty acid esters and particularly pentaerythritol menstruate are known as deforming compounds (of e.g. Austrian patent 330,728 and US
patent 2,715,613). In addition, examples 2 of Austrian 10 patent 330,728 describes a deforming agent dispersion which, in a non-aqueous medium, contains 820 parts by weight of a long chain alcohol, namely isotridecyl alcohol, as well as further conventional constituents, apart from 70 parts by weight of pentaerythritol menstruate. However, this combination of pentaerythritol menstruate and isotridecyl alcohol in the form of a non-aqueous dispersion has an inferior deforming action to a corresponding combination of oxystearyl monobehenate and isotridecyl alcohol. Moreover, the isotridecyl alcohol according to Austrian patent 330,728 mainly acts as a dispersion medium and can also be replaced by mineral oils. Example No. 2b of this patent has been reworked and has been found by far inferior to the present invention.
Although in particular the deforming systems according to German patent 2,157,033 offer very satisfactory results, there is still a considerable need for improved products and particularly those which can be more universally used both for deforming and decorating purposes.
a OBJECTS OF THE INVENTION
-Therefore it is an object of this invention to provide agents for deforming and decorating aqueous systems, which are more effective than those hitherto known, i.e.
which have a better decorating and deforming action over a wide fringe, or which can be used in smaller quantities, so that the probability of undesired effects on the quality of the end product is still further reduced.
It is a further object of this invention to provide agents for deforming and decorating aqueous systems which are more universally usable and are e.g. also suitable for drilling muds.
These and further objects will become apparent as the description of the invention proceeds.
SUMMARY OF THE INVENTION
The invention provides agents for deforming and decorating aqueous systems based on dispersions containing C14 to C26-alcohols and per so known emulsifiers, characterized in that the dispersions also contain one or more fatty acid esters of polyhydric alcohols, having at least 4 hydroxyl groups, the number of carbon atoms in the fatty acid or acids being 14 or higher and preferably 16 to 18.
The invention further provides the use of such agents for deforming and decorating aqueous systems.
1~3~)'70 DETAILED DESCRIPTION OF INVENTION
The present invention is directed to agents for 5 deforming and decorating aqueous systems based on dispersions of the type as described herein and in the appended claims. Furthermore the invention is directed to the use of these agents for deforming and decorating aqueous systems.
According to the invention, it has surprisingly been found that there is a marked synergistic action, if mixtures of fatty alcohols and fatty acid esters of polyhydric alcohols, containing at least 4 hydroxyl groups, 15 are used in the form of aqueous dispersions as agents for deforming and decorating aqueous systems. The deforming and decorating action of these mixtures is not only much better than that of the individual components, but is also better than the best commercially available agents. A
20 particular advantage of the agents according to the invention is that they can be used in small quantities and provide an excellent decorating and deforming action over a wide fringe. In addition, the tests performed have shown that the agents according to the invention have wide 25 applicability and are suitable for decorating and deforming aqueous systems in e.g. the paints, pulp, paper, foods and drilling industry, as well as for decorating and deforming transport water in the processing of sugar beet and potatoes, as well as waste water or sewage. Special examples 30 for the use of the agents according to the invention are inter aria fibrous suspensions such as paper pulps, clay dispersions, aqueous paint systems, drilling muds, waste water, sewage and the aforementioned transport water for sugar beet and potato processing.
The agents according to the invention are prepared in that the C14 to Calculus are melted together with the fatty acid esters of the polyhydric alcohols in water at temperatures above the melting points thereof and generally 5 at approximately 75nc. Alternatively, the alcohols and esters can be melted together in a preliminary stage and then are introduced into hot water. After adding emulsifiers, the mixture is then homogenized by per so known equipment and is cooled to ambient temperature, accompanied 10 by thorough mixing. After homogenization additional emulsifiers may be added to improve, if desired, the rheologial properties of the agents according the invention.
Thickening agents may also be used for the same purpose, added either before or after homogenization. Suitable 15 emulsifiers are those known to the expert, preferably anionic and non ionic emulsifiers, such as ethoxylated nonyl phenol, Al Kane sulfonates, alkyd aureole sulphonic acid salts and the like. As thickening agents a variety of different product types may be used. These thickening agents are well 20 known to the expert and include for example polyacrylates, alginates, bentonite, car boxy methyl cellulose and guard gum.
The mean arithmetic particle size of the dispersed, water-insoluble substances, which is determined according to the Courter Counter method (of Special Technical Publication 25 No. 234 of the American Society for Testing Materials, "Electronic Size Analysis of Sub sieve Particles by Flowing Through a Small Liquid Resistor", by Robert H. Berg, 1958, pp. 1-5), is advantageously in the range of 1 to 6 em and particularly approximately 2 to 3 em.
In order that the synergistic action of the mixture of fatty alcohols and fatty acid esters of polyhydric alcohols, containing at least 4 hydroxyl groups, is as marked as possible, it must be ensured that the 35 correct weight ratio between the components of this mixture is maintained. Admittedly, the optimum weight ratio of the components of the mixture depends on the fatty alcohols and esters used, but it can generally be stated that a weight ratio of fatty alcohols to fatty acid esters of polyhydric 5 alcohols of 2:1 to 10:1 and preferably 3.5:1 to 4.5:1 is preferred. The solids content of the dispersions according to the invention is conventionally 10 to 400 by weight. The lower limit is mainly Fixed by purely economic consideration, whilst solids contents above OWE by weight 10 make it more difficult to handle the dispersions. Preference is given to solids contents of 20 to OWE by weight.
The quantity of the agents according to the invention necessary for good decorating and deforming is obviously 15 dependent on the aqueous system to be decorated and deformed and can correspondingly differ within wide limits. Thus, in decorating and deforming paper making fiber suspensions, very good results are obtained with only a few Pam of the agents according to the invention, whereas e.g. when 20 decorating and deforming drilling muds, higher concentrations are generally required. The in each case optimum concentration of the agents according to the invention can easily be determined by a few tests. In general, the quantities known for other agents from the 25 prior art and frequently even smaller quantities can be used.
The C14 to Calculus used according to the invention constitute conventional constituents of deforming and dirtying agents and are commercially available. The esters which are also present in the agents according to the invention are esterification products of fatty acids with 14 or more carbon atoms and polyhydric alcohols, containing at least 4 hydroxyl groups. However, preference is given to esters of C16 to C18-fatty acids. In practice technical grade fatty acids (C14 to C18) can be used wherein e.g. the content of Clue is less than about 20 mold, the Clue content is from 40 to 60 Molly and the balance is Clue. In particular, pentaerythritol, dipentaerythritol and ditrimethylol propane have proved suitable as polyhydric alcohols containing at 5 least 4 hydroxyl groups. Dipentaerythritol and ditrimethylol propane are divers of pentaerythritol and trimethylol propane, in which the monomers are linked via an ether bond.
Thus, dipentaerythritol has 6 hydroxyl groups, whilst ditrimethylol propane has 4 hydroxyl groups. On the basis of 10 the tests performed, partial esters of the aforementioned fatty acids and alcohols have proved to be particularly suitable. Thus, it has been found that a partial pentaerythritol Starkey acid ester, which largely consists of pentaerythritol distrait, gives better results than 15 pentaeryhtritol menstruate or pentaerythritol tetrastearate. Obviously, the partial esters are never unitary compounds, because as a result of the chemical equilibrium, products esterified to a varying degree always appear side by side, i.e. the aforementioned pentaerythritol 20 distrait contains at least pentaerythritol menstruate and pentaerythritol tristearate as well and probably small amounts of pentaeryhtritol and pentaerythritol tetrastearate. Thus, within the scope of the present invention, the term partial ester means that it is the main 25 component of the ester mixture present due to the chemical equilibrium. Such partial esters are commercially available.
Although this is not generally necessary, the agents according to the invention can obviously also contain 30 further constituents acting in a deforming and decorating manner. Such additional constituents, such as e.g. mineral oil, are well known to the expert, so that there is no need to give further details (of e.g. the aforementioned prior art). When using such additional deforming and decorating 35 constituents, it is necessary to ensure that the _ 9 _ effectiveness of the synergistic mixture according to the invention is not impaired or significantly reduced. Thus, such known constituents are generally only used in minor amounts.
The following examples are given for illustrative purposes only and are not meant to be a limitation on the subject invention. In all cases, unless otherwise noted, all parts and percentages are by weight.
Example l lo parts by weight of Clue to Calculus are melted together with 5 parts by weight of the aforementioned 15 partial pentaerythritol Stewart, whose essential component is pentaeryhtritol distrait, in 75 parts by weight of water at 75C. After adding 0.5 parts by weight of ethoxylated nonyl phenol and 0.5 parts by weight of Al Kane sulphonates as emulsifiers, the mixture is homogenized and 20 then cooled to 25C, accompanied by further thorough mixing.
Comparison Example l 24 parts by weight of Clue to Calculus are melted in 75 parts by weight of water at 75C, followed by the addition 25 of the same emulsifiers as in example l. The following homogenization and cooling also take place as in example l.
Comparison Example 2 24 parts by weight of the pentaerythritol Stewart also used 30 in example l are melted in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in example l. The following homogenization and cooling also take place according to example l.
ox - in Comparison Example 3 lo parts by weight of Clue to Calculus and 5 parts by weight of ethylene glycol distrait are melted together in 75 parts by weight of water at 75C. After adding 0.5 parts 5 by weight of ethoxylated nonyl phenol and 0.5 parts by weight of sodium alkali aureole sulphonate as emulsifiers, the mixture is homogenized and then cooled to 25C, accompanied by thorough mixing.
10 Comparison Example 4 lo parts by weight of Clue to Calculus and 5 parts of ethylene glycol distrait are melted together in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. The following 15 homogenization and cooling take place in accordance with example l or comparison example 3.
Comparison Example 5 lo parts by weight of Clue to Calculus and 5 parts by 20 weight of tallow are melted together in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. The homogenization and cooling of the mixture take place as in example l or comparison example 3.
Example 2 19 parts by weight of Clue to Calculus and 5 parts by weight of the pentaerythritol Stewart used in example l are melted together in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. Homogenization and cooling of the mixture take place in the manner described in example l or comparison example 3.
Example 3 19 parts by weight of C16 to Calculus and 5 parts by weight of the pentaerythritol Stewart used in example 1 are melted in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. Homogenization and cooling of the mixture takes place as in example 1 or comparison example 3.
The average arithmetic particle size of the dispersions prepared according to examples 1 to 3 and comparison examples 1 to 5 is determined by the Courter counter method using a computer and is 2.2 em in all the emulsions.
Example 4 In order to investigate the effectiveness of the dispersions prepared according to examples 1 to 3 and comparison examples 1 to 5, a test furnish was prepared from 0.5 parts by weight of bleached sulfite pulp, 0.02 parts by weight of lignosulphonate, 0.004 parts by weight of rosin acids (sizing agents) and 99.47 parts by weight of tap water. In a few cases, the sulfite pulp is replaced by newspaper waste and cellulose.
The air content of the thus prepared test furnish is measured by means of a special Plexiglass foam box, equipped with a return line, a circulating pump and a sampling and measuring device. In each test, 10 liters of substance composition are used and are circulated by means of the circulating pump. Reference is made to Norsk Skogindustri, Vol. 21, No. 12, pp. 503-506, 1967 in connection with the sampling and measuring device and the air content determination carried out with it. When using this device, it is possible to directly read off the air content as a percentage from the calibrated unit of I
measurement. The tests are performed in such a way that the foam box is filled with the furnish, the pump is put into operation and after a certain time, the decorating and deforming agent is added. The tests are normally performed 5 at a pH-value of 7 and a temperature of 35C. The air content is then determined as a function of the time. The results are obtained and graphically represented, by plotting the air content versus time.
The dispersions according to example 1 and 10 comparison examples 1 and 2 are investigated in the aforementioned manner. The quantity of active substance used (based on the solids content) is in each case 16 Pam, the temperature is 35C and the pH-value is 7Ø The test results given in graph form in Foggily show the considerable 15 synergistic action of the mixture of C18 to Calculus and pentaerythritol struts compared with the individual components.
The dispersions of example 2 and comparison 20 examples 3 to 5 are investigated in the same way, i.e. the concentration is in each case 16 Pam, the temperature 35C
and the pH-value is 7Ø The results given in Fugue clearly show the superiority of the invented mixture of fatty alcohol and pentarerythritol Stewart.
In addition, three commercial products are investigated in the same way and compared with the dispersion according to example 2. The commercial products are based on (a) Cog to Calculus (solution and not 30 dispersion), (b) a mixture of fatty alcohols and paraffin wax (dispersion, particle size approx. 1 em) and (c) fatty alcohols (dispersion, particle size approx. 2 to 3 em). The compositions given for commercial products (b) and (c) are based on empirical investigations which are subject to 35 uncertainty. As is clear from the results given in Fig-3, the dispersions according to example 2 are far superior to the commercial products.
Example 5 5 Using the dispersion according to example 3, the influence of the pH-value is investigated using the process descried in example 4. Tests are performed at pH-values of 4,5, 7 and 10. For comparison purposes, the corresponding tests are carried out with a commercial aqueous dispersion (probably a dispersion of a mixture of fatty alcohol and glycerol Minnesota-rate, particle size approx. 2 to 3 em), which is one of the best commercially available decorating agents. In each case, û.6 9 of both products are used for each measurement. The test results given in graph form in Fig. 4 show the 15 excellent decorating action of the dispersion according to the invention in the investigated fringe, compared with the commercially available product.
Example 6 The following procedure has been adopted for investigating the suitability of the agents according to the invention for drilling muds. A mud is prepared from 8 parts by weight of bentonite, parts by weight of sea salt, 1.5 parts by weight of lignosulphonate and 87.5 parts by weight of tap 25 water, whose pH-value is adjusted to 9.5. The resulting mud is mixed for 15 minutes at high speed using a domestic mixer, after which the mud is transferred into a measuring cylinder. The air content as ml of air/lOOml of mud is calculated after a given time from the difference of the density determined before and after mixing.
Whereas, without addition, the air content is 37.9 ml/100 ml of mud, in the case of adding 0.5 of the dispersion according to example 3, an air content of 19.1 ml/100 ml is measured. The olmærcial product used in 9(~'7f~
example 5 is ineffective.
Comparative Example Example 2b of Austrian patent 330728 was prepared as 5 specified. Commercial materials were used except the reaction product from isotridecylalcohol + 2 moles ethylenoxide + 4 moles propylenoxide. This material was prepared according to standard methods known to the experts.
The formulated product was tested using the process 10 described in example 4. The test result given in graph form Fugue shows the inferior decorating effect of this product compared with the present invention.
The present invention relates to agents for 5 deforming and decorating aqueous systems based on aqueous dispersions, which contain conventional deforming and decorating alcohols, specific fatty acid esters of polyhydric alcohols and conventional emulsifiers.
In industrial processes performed in aqueous media, the latter frequently have high air contents and/or disturbing foams frequently occur, thereby impairing the performance of the process and the quality of the products obtained. Thus, a number of processes and agents for 15 decorating and deforming aqueous systems have already been proposed. Therefore, the literature and particularly the patent literature dealing with this subject is very comprehensive. As this literature is well known to the expert, it will be sufficient at this point to refer in 20 exemplified manner to the summary description given in German patent 2,157,033.
German patent 2,157,033 proposes aqueous emulsions (or more correctly dispersions) for deforming aqueous 25 systems containing conventional deforming C12 to C22-alkanols and/or C12 to C22-fatty acid esters of dihydric or trihydric alcohols, as well as up to OWE based on the weight of the non-aqueous components, of paraffin oils and/or C12 to C22-fatty acids as foam removers, as well as 30 per so known additives of surfactants of an anionic, cat ionic or non ionic type as emulsifiers. According to the teaching of this patent specification, these per so known emulsions are relatively universally usable, provided that the average particle size of the emulsified, water-insoluble 35 substances is 4 to em The decorating and deforming agents according to German patent 2,157,033 are widely used in practice, but have proved to be ineffective in drilling muds.
Apart from the deforming compounds referred to in German patent 2,157,033, pentaerythritol fatty acid esters and particularly pentaerythritol menstruate are known as deforming compounds (of e.g. Austrian patent 330,728 and US
patent 2,715,613). In addition, examples 2 of Austrian 10 patent 330,728 describes a deforming agent dispersion which, in a non-aqueous medium, contains 820 parts by weight of a long chain alcohol, namely isotridecyl alcohol, as well as further conventional constituents, apart from 70 parts by weight of pentaerythritol menstruate. However, this combination of pentaerythritol menstruate and isotridecyl alcohol in the form of a non-aqueous dispersion has an inferior deforming action to a corresponding combination of oxystearyl monobehenate and isotridecyl alcohol. Moreover, the isotridecyl alcohol according to Austrian patent 330,728 mainly acts as a dispersion medium and can also be replaced by mineral oils. Example No. 2b of this patent has been reworked and has been found by far inferior to the present invention.
Although in particular the deforming systems according to German patent 2,157,033 offer very satisfactory results, there is still a considerable need for improved products and particularly those which can be more universally used both for deforming and decorating purposes.
a OBJECTS OF THE INVENTION
-Therefore it is an object of this invention to provide agents for deforming and decorating aqueous systems, which are more effective than those hitherto known, i.e.
which have a better decorating and deforming action over a wide fringe, or which can be used in smaller quantities, so that the probability of undesired effects on the quality of the end product is still further reduced.
It is a further object of this invention to provide agents for deforming and decorating aqueous systems which are more universally usable and are e.g. also suitable for drilling muds.
These and further objects will become apparent as the description of the invention proceeds.
SUMMARY OF THE INVENTION
The invention provides agents for deforming and decorating aqueous systems based on dispersions containing C14 to C26-alcohols and per so known emulsifiers, characterized in that the dispersions also contain one or more fatty acid esters of polyhydric alcohols, having at least 4 hydroxyl groups, the number of carbon atoms in the fatty acid or acids being 14 or higher and preferably 16 to 18.
The invention further provides the use of such agents for deforming and decorating aqueous systems.
1~3~)'70 DETAILED DESCRIPTION OF INVENTION
The present invention is directed to agents for 5 deforming and decorating aqueous systems based on dispersions of the type as described herein and in the appended claims. Furthermore the invention is directed to the use of these agents for deforming and decorating aqueous systems.
According to the invention, it has surprisingly been found that there is a marked synergistic action, if mixtures of fatty alcohols and fatty acid esters of polyhydric alcohols, containing at least 4 hydroxyl groups, 15 are used in the form of aqueous dispersions as agents for deforming and decorating aqueous systems. The deforming and decorating action of these mixtures is not only much better than that of the individual components, but is also better than the best commercially available agents. A
20 particular advantage of the agents according to the invention is that they can be used in small quantities and provide an excellent decorating and deforming action over a wide fringe. In addition, the tests performed have shown that the agents according to the invention have wide 25 applicability and are suitable for decorating and deforming aqueous systems in e.g. the paints, pulp, paper, foods and drilling industry, as well as for decorating and deforming transport water in the processing of sugar beet and potatoes, as well as waste water or sewage. Special examples 30 for the use of the agents according to the invention are inter aria fibrous suspensions such as paper pulps, clay dispersions, aqueous paint systems, drilling muds, waste water, sewage and the aforementioned transport water for sugar beet and potato processing.
The agents according to the invention are prepared in that the C14 to Calculus are melted together with the fatty acid esters of the polyhydric alcohols in water at temperatures above the melting points thereof and generally 5 at approximately 75nc. Alternatively, the alcohols and esters can be melted together in a preliminary stage and then are introduced into hot water. After adding emulsifiers, the mixture is then homogenized by per so known equipment and is cooled to ambient temperature, accompanied 10 by thorough mixing. After homogenization additional emulsifiers may be added to improve, if desired, the rheologial properties of the agents according the invention.
Thickening agents may also be used for the same purpose, added either before or after homogenization. Suitable 15 emulsifiers are those known to the expert, preferably anionic and non ionic emulsifiers, such as ethoxylated nonyl phenol, Al Kane sulfonates, alkyd aureole sulphonic acid salts and the like. As thickening agents a variety of different product types may be used. These thickening agents are well 20 known to the expert and include for example polyacrylates, alginates, bentonite, car boxy methyl cellulose and guard gum.
The mean arithmetic particle size of the dispersed, water-insoluble substances, which is determined according to the Courter Counter method (of Special Technical Publication 25 No. 234 of the American Society for Testing Materials, "Electronic Size Analysis of Sub sieve Particles by Flowing Through a Small Liquid Resistor", by Robert H. Berg, 1958, pp. 1-5), is advantageously in the range of 1 to 6 em and particularly approximately 2 to 3 em.
In order that the synergistic action of the mixture of fatty alcohols and fatty acid esters of polyhydric alcohols, containing at least 4 hydroxyl groups, is as marked as possible, it must be ensured that the 35 correct weight ratio between the components of this mixture is maintained. Admittedly, the optimum weight ratio of the components of the mixture depends on the fatty alcohols and esters used, but it can generally be stated that a weight ratio of fatty alcohols to fatty acid esters of polyhydric 5 alcohols of 2:1 to 10:1 and preferably 3.5:1 to 4.5:1 is preferred. The solids content of the dispersions according to the invention is conventionally 10 to 400 by weight. The lower limit is mainly Fixed by purely economic consideration, whilst solids contents above OWE by weight 10 make it more difficult to handle the dispersions. Preference is given to solids contents of 20 to OWE by weight.
The quantity of the agents according to the invention necessary for good decorating and deforming is obviously 15 dependent on the aqueous system to be decorated and deformed and can correspondingly differ within wide limits. Thus, in decorating and deforming paper making fiber suspensions, very good results are obtained with only a few Pam of the agents according to the invention, whereas e.g. when 20 decorating and deforming drilling muds, higher concentrations are generally required. The in each case optimum concentration of the agents according to the invention can easily be determined by a few tests. In general, the quantities known for other agents from the 25 prior art and frequently even smaller quantities can be used.
The C14 to Calculus used according to the invention constitute conventional constituents of deforming and dirtying agents and are commercially available. The esters which are also present in the agents according to the invention are esterification products of fatty acids with 14 or more carbon atoms and polyhydric alcohols, containing at least 4 hydroxyl groups. However, preference is given to esters of C16 to C18-fatty acids. In practice technical grade fatty acids (C14 to C18) can be used wherein e.g. the content of Clue is less than about 20 mold, the Clue content is from 40 to 60 Molly and the balance is Clue. In particular, pentaerythritol, dipentaerythritol and ditrimethylol propane have proved suitable as polyhydric alcohols containing at 5 least 4 hydroxyl groups. Dipentaerythritol and ditrimethylol propane are divers of pentaerythritol and trimethylol propane, in which the monomers are linked via an ether bond.
Thus, dipentaerythritol has 6 hydroxyl groups, whilst ditrimethylol propane has 4 hydroxyl groups. On the basis of 10 the tests performed, partial esters of the aforementioned fatty acids and alcohols have proved to be particularly suitable. Thus, it has been found that a partial pentaerythritol Starkey acid ester, which largely consists of pentaerythritol distrait, gives better results than 15 pentaeryhtritol menstruate or pentaerythritol tetrastearate. Obviously, the partial esters are never unitary compounds, because as a result of the chemical equilibrium, products esterified to a varying degree always appear side by side, i.e. the aforementioned pentaerythritol 20 distrait contains at least pentaerythritol menstruate and pentaerythritol tristearate as well and probably small amounts of pentaeryhtritol and pentaerythritol tetrastearate. Thus, within the scope of the present invention, the term partial ester means that it is the main 25 component of the ester mixture present due to the chemical equilibrium. Such partial esters are commercially available.
Although this is not generally necessary, the agents according to the invention can obviously also contain 30 further constituents acting in a deforming and decorating manner. Such additional constituents, such as e.g. mineral oil, are well known to the expert, so that there is no need to give further details (of e.g. the aforementioned prior art). When using such additional deforming and decorating 35 constituents, it is necessary to ensure that the _ 9 _ effectiveness of the synergistic mixture according to the invention is not impaired or significantly reduced. Thus, such known constituents are generally only used in minor amounts.
The following examples are given for illustrative purposes only and are not meant to be a limitation on the subject invention. In all cases, unless otherwise noted, all parts and percentages are by weight.
Example l lo parts by weight of Clue to Calculus are melted together with 5 parts by weight of the aforementioned 15 partial pentaerythritol Stewart, whose essential component is pentaeryhtritol distrait, in 75 parts by weight of water at 75C. After adding 0.5 parts by weight of ethoxylated nonyl phenol and 0.5 parts by weight of Al Kane sulphonates as emulsifiers, the mixture is homogenized and 20 then cooled to 25C, accompanied by further thorough mixing.
Comparison Example l 24 parts by weight of Clue to Calculus are melted in 75 parts by weight of water at 75C, followed by the addition 25 of the same emulsifiers as in example l. The following homogenization and cooling also take place as in example l.
Comparison Example 2 24 parts by weight of the pentaerythritol Stewart also used 30 in example l are melted in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in example l. The following homogenization and cooling also take place according to example l.
ox - in Comparison Example 3 lo parts by weight of Clue to Calculus and 5 parts by weight of ethylene glycol distrait are melted together in 75 parts by weight of water at 75C. After adding 0.5 parts 5 by weight of ethoxylated nonyl phenol and 0.5 parts by weight of sodium alkali aureole sulphonate as emulsifiers, the mixture is homogenized and then cooled to 25C, accompanied by thorough mixing.
10 Comparison Example 4 lo parts by weight of Clue to Calculus and 5 parts of ethylene glycol distrait are melted together in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. The following 15 homogenization and cooling take place in accordance with example l or comparison example 3.
Comparison Example 5 lo parts by weight of Clue to Calculus and 5 parts by 20 weight of tallow are melted together in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. The homogenization and cooling of the mixture take place as in example l or comparison example 3.
Example 2 19 parts by weight of Clue to Calculus and 5 parts by weight of the pentaerythritol Stewart used in example l are melted together in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. Homogenization and cooling of the mixture take place in the manner described in example l or comparison example 3.
Example 3 19 parts by weight of C16 to Calculus and 5 parts by weight of the pentaerythritol Stewart used in example 1 are melted in 75 parts by weight of water at 75C, followed by the addition of the same emulsifiers as in comparison example 3. Homogenization and cooling of the mixture takes place as in example 1 or comparison example 3.
The average arithmetic particle size of the dispersions prepared according to examples 1 to 3 and comparison examples 1 to 5 is determined by the Courter counter method using a computer and is 2.2 em in all the emulsions.
Example 4 In order to investigate the effectiveness of the dispersions prepared according to examples 1 to 3 and comparison examples 1 to 5, a test furnish was prepared from 0.5 parts by weight of bleached sulfite pulp, 0.02 parts by weight of lignosulphonate, 0.004 parts by weight of rosin acids (sizing agents) and 99.47 parts by weight of tap water. In a few cases, the sulfite pulp is replaced by newspaper waste and cellulose.
The air content of the thus prepared test furnish is measured by means of a special Plexiglass foam box, equipped with a return line, a circulating pump and a sampling and measuring device. In each test, 10 liters of substance composition are used and are circulated by means of the circulating pump. Reference is made to Norsk Skogindustri, Vol. 21, No. 12, pp. 503-506, 1967 in connection with the sampling and measuring device and the air content determination carried out with it. When using this device, it is possible to directly read off the air content as a percentage from the calibrated unit of I
measurement. The tests are performed in such a way that the foam box is filled with the furnish, the pump is put into operation and after a certain time, the decorating and deforming agent is added. The tests are normally performed 5 at a pH-value of 7 and a temperature of 35C. The air content is then determined as a function of the time. The results are obtained and graphically represented, by plotting the air content versus time.
The dispersions according to example 1 and 10 comparison examples 1 and 2 are investigated in the aforementioned manner. The quantity of active substance used (based on the solids content) is in each case 16 Pam, the temperature is 35C and the pH-value is 7Ø The test results given in graph form in Foggily show the considerable 15 synergistic action of the mixture of C18 to Calculus and pentaerythritol struts compared with the individual components.
The dispersions of example 2 and comparison 20 examples 3 to 5 are investigated in the same way, i.e. the concentration is in each case 16 Pam, the temperature 35C
and the pH-value is 7Ø The results given in Fugue clearly show the superiority of the invented mixture of fatty alcohol and pentarerythritol Stewart.
In addition, three commercial products are investigated in the same way and compared with the dispersion according to example 2. The commercial products are based on (a) Cog to Calculus (solution and not 30 dispersion), (b) a mixture of fatty alcohols and paraffin wax (dispersion, particle size approx. 1 em) and (c) fatty alcohols (dispersion, particle size approx. 2 to 3 em). The compositions given for commercial products (b) and (c) are based on empirical investigations which are subject to 35 uncertainty. As is clear from the results given in Fig-3, the dispersions according to example 2 are far superior to the commercial products.
Example 5 5 Using the dispersion according to example 3, the influence of the pH-value is investigated using the process descried in example 4. Tests are performed at pH-values of 4,5, 7 and 10. For comparison purposes, the corresponding tests are carried out with a commercial aqueous dispersion (probably a dispersion of a mixture of fatty alcohol and glycerol Minnesota-rate, particle size approx. 2 to 3 em), which is one of the best commercially available decorating agents. In each case, û.6 9 of both products are used for each measurement. The test results given in graph form in Fig. 4 show the 15 excellent decorating action of the dispersion according to the invention in the investigated fringe, compared with the commercially available product.
Example 6 The following procedure has been adopted for investigating the suitability of the agents according to the invention for drilling muds. A mud is prepared from 8 parts by weight of bentonite, parts by weight of sea salt, 1.5 parts by weight of lignosulphonate and 87.5 parts by weight of tap 25 water, whose pH-value is adjusted to 9.5. The resulting mud is mixed for 15 minutes at high speed using a domestic mixer, after which the mud is transferred into a measuring cylinder. The air content as ml of air/lOOml of mud is calculated after a given time from the difference of the density determined before and after mixing.
Whereas, without addition, the air content is 37.9 ml/100 ml of mud, in the case of adding 0.5 of the dispersion according to example 3, an air content of 19.1 ml/100 ml is measured. The olmærcial product used in 9(~'7f~
example 5 is ineffective.
Comparative Example Example 2b of Austrian patent 330728 was prepared as 5 specified. Commercial materials were used except the reaction product from isotridecylalcohol + 2 moles ethylenoxide + 4 moles propylenoxide. This material was prepared according to standard methods known to the experts.
The formulated product was tested using the process 10 described in example 4. The test result given in graph form Fugue shows the inferior decorating effect of this product compared with the present invention.
Claims (19)
1. Agents for defoaming and deaerating aqueous systems based on dispersions containing C14 to C26-alcohols and per se known emulsifiers, characterized in that the dispersions also contain one or more fatty acid esters of polyhydric alcohols, having at least 4 hydroxyl groups, the number of carbon atoms in the fatty acid or acids being 14 or higher and preferably 16 to 18.
2. Agents according to claim 1, characterized in that the dispersions contain fatty acid esters of pentaerythritol, dipentaerythritol and/or ditrimethylol propane.
3. Agents according to claim 1, characterized in that the dispersions contain one or more partial fatty acid esters of polyhydric alcohols, having at least 4 hydroxyl groups.
4. Agents according to claim 3, characterized in that the dispersions contain a partial pentaerythritol stearic acid ester, which largely consists of pentaerythritol distearate.
5. Agents according to claim 1, characterized in that the weight ratio of alcohols to esters is 2:1 to 10:1.
6. Agents according to claim 5 in which the said ratio is 3.5:1 to 4.5:1.
7. Agents according to claim 1, characterized in that the mean particle size of the dispersed, water-insoluble substances is 1 to 6.
8. Agents according to claim 7 in which the said mean particle size is 2 to 3 µm.
9. Use of the agents according to claim 1 for defoaming and deaerating aqueous systems.
10. Use of the agents according to claim 2 for defoaming and deaerating aqueous systems.
11. Use of the agents according to claim 3 for defoaming and deaerating aqueous systems.
12. Use of the agents according to claim 4 for defoaming and deaerating aqueous systems.
13. Use of the agents according to claim 5 for defoaming and deaerating aqueous systems.
14. Use of the agents according to claim 6 for defoaming and deaerating aqueous systems.
15. Use of the agents according to claim 7 for defoaming and deaerating aqueous systems.
16. Use of the agents according to claim 8 for defoaming and deaerating aqueous systems.
17. Use according to claim 9, 10 or 11, characterized in that the aqueous systems involved are in the paints, pulp, paper, foods or drilling industry, or can be transport waters used in the processing of sugar beet and potatoes, or can be waste water or sewage.
18. Use according to claim 12, 13 or 14, characterized in that the aqueous systems involved are in the paints, pulp, paper, foods or drilling industry, or can be transport waters used in the processing of sugar beet and potatoes, or can be waste water or sewage.
19. Use according to claim 15 or 16 characterized in that the aqueous systems involved are in the paints, pulp, paper, foods or drilling industry, or can be transport waters used in the processing of sugar beet and potatoes, or can be waste water or sewage.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8303890A SE443092B (en) | 1983-07-07 | 1983-07-07 | MEASURES FOR DEFINING AND DEHIBITING Aqueous systems based on aqueous dispersions and using the agent |
| SE8303890.1 | 1983-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1239070A true CA1239070A (en) | 1988-07-12 |
Family
ID=20351920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000458161A Expired CA1239070A (en) | 1983-07-07 | 1984-07-05 | Agents for defoaming and deaerating aqueous systems and the use thereof |
Country Status (5)
| Country | Link |
|---|---|
| CA (1) | CA1239070A (en) |
| DE (1) | DE3423994A1 (en) |
| FR (1) | FR2548548B1 (en) |
| GB (1) | GB2142837B (en) |
| SE (1) | SE443092B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3911238A1 (en) * | 1989-04-07 | 1990-10-11 | Henkel Kgaa | OLEOPHILE ALCOHOLS AS A COMPONENT OF INVERT DRILLING |
| DE19505178A1 (en) * | 1995-02-16 | 1996-08-22 | Henkel Kgaa | Dispersions with optionally esterified (poly) glycerol polyglycol ethers |
| DE19508938A1 (en) * | 1995-03-13 | 1996-09-19 | Basf Ag | Defoamers and / or deaerators for aqueous media that tend to foam |
| AU2003227260A1 (en) | 2002-03-28 | 2003-10-13 | The Nisshin Oillio Group, Ltd. | Fine particle dispersant, and cosmetics, coating materials, inks, storage materials and lubricants, containing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE791209A (en) * | 1971-11-17 | 1973-05-10 | Basf Ag | ANTI-FOAM AQUEOUS EMULSIONS |
| US4303549A (en) * | 1979-10-18 | 1981-12-01 | Drew Chemical Corporation | Liquid defoamer and defoaming process |
| JPS5763108A (en) * | 1980-09-30 | 1982-04-16 | Riken Vitamin Co Ltd | Antifoaming agent |
-
1983
- 1983-07-07 SE SE8303890A patent/SE443092B/en not_active IP Right Cessation
-
1984
- 1984-06-29 DE DE19843423994 patent/DE3423994A1/en not_active Withdrawn
- 1984-07-05 CA CA000458161A patent/CA1239070A/en not_active Expired
- 1984-07-05 GB GB08417176A patent/GB2142837B/en not_active Expired
- 1984-07-06 FR FR8410802A patent/FR2548548B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| SE8303890D0 (en) | 1983-07-07 |
| GB2142837A (en) | 1985-01-30 |
| FR2548548A1 (en) | 1985-01-11 |
| SE443092B (en) | 1986-02-17 |
| FR2548548B1 (en) | 1989-09-15 |
| DE3423994A1 (en) | 1985-01-17 |
| SE8303890L (en) | 1985-01-08 |
| GB2142837B (en) | 1987-02-11 |
| GB8417176D0 (en) | 1984-08-08 |
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