CA1169735A - Process for the production of an anion exchanger, and a use of same - Google Patents
Process for the production of an anion exchanger, and a use of sameInfo
- Publication number
- CA1169735A CA1169735A CA000393124A CA393124A CA1169735A CA 1169735 A CA1169735 A CA 1169735A CA 000393124 A CA000393124 A CA 000393124A CA 393124 A CA393124 A CA 393124A CA 1169735 A CA1169735 A CA 1169735A
- Authority
- CA
- Canada
- Prior art keywords
- cellulose
- reaction
- anion exchanger
- ion exchanger
- waste water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Treatment Of Water By Ion Exchange (AREA)
Abstract
Abstract of the Disclosure.
An anion exchanger is produced by treating cellulose or a cellulose derivative with a polyethylene imine solution of at least 1% by weight in an aqueous medium at a pH-value between 2 and 6, preferab-ly between 4 and 5, and recovering the ion exchanger from the re-action mixture. The reaction between cellulose or cellulose derivative and polyethylene imine can take place at ambient temperature, but may be promoted by using a temperature of 40-90° C, preferably 60-70°C.
Preferred cellulose derivatives for use as starting material are sul-phonated lignocellulose or a cellulose material, e.g. bark which has been treated in separate steps with an alkali hydroxide solution and with sulphuric acid. The anion exchanger can be regenerated by el?-tion with sodium hydroxide and reactivated by treatment with poly-ethylene imine.
The anion exchanger is suitable for the purification of waste water and can be produced at low cost.
An anion exchanger is produced by treating cellulose or a cellulose derivative with a polyethylene imine solution of at least 1% by weight in an aqueous medium at a pH-value between 2 and 6, preferab-ly between 4 and 5, and recovering the ion exchanger from the re-action mixture. The reaction between cellulose or cellulose derivative and polyethylene imine can take place at ambient temperature, but may be promoted by using a temperature of 40-90° C, preferably 60-70°C.
Preferred cellulose derivatives for use as starting material are sul-phonated lignocellulose or a cellulose material, e.g. bark which has been treated in separate steps with an alkali hydroxide solution and with sulphuric acid. The anion exchanger can be regenerated by el?-tion with sodium hydroxide and reactivated by treatment with poly-ethylene imine.
The anion exchanger is suitable for the purification of waste water and can be produced at low cost.
Description
The invention relates to a process for the production of an anion exchanger which is particularly suitable for the treatment of waste water.
The treatment of municipal and industrial waste water is be-5 coming an increasing problem, especially in industrialized countries.It is therefore technologically important to develop processes which give a high efficiency at relative low cost for the treatment of waste water which besides protein and heavy metals contains refractory components. Proteins can be treated on biological units, but often the 10 materials are so valuable that it would be natural to consider a reco-very process.
Proteins, polypeptides and amino acids can be removed by chemical precipitation. As precipitants are used lignin sulphuric acid and dodecylbenzene sulphonic acid, and others.
However, only very high molecular weight proteins are pre-cipitated and compounds such as proteins with medium and lower molecular weight, polypeptides and amino acids are not removed by this process.
It would therefore be desirable to have an ion exchanger 20 available which can remove such compounds and can therefore be used for the treatment of waste water, which has been subjected to the precipitation treatment. Examples of waste water for which such a combined treatment may be advantageous is such from fish filletting factories, dairies, slaughterhouses and other food processing plants.
25 This removal is furthermore of interest for the recirculation of water in fish farms.
A number of cellulose ion exchangers are already on the market. Examples are cellulose sulphate esters produced by reacting cellulose with SO3, and also cellulose phosphate esters. These are 30 capable of solving the above mentioned problem, but all these ion exchangers are prohibitively expensive.
It is the object of the invention to provide a process for the production of ion exchangers which have high efficiency in -the treatment of waste water and can be produced at the lowest possible 35 cost. Particularly, these ion exchangers should be capable of removing anionic organic compounds as well as pro-teins and other nitrogen compounds from the waste water. Moreover, the ion exchanger should be capable of regeneration in order to reduce the problem of disposing of consumed ion exchanger material to a minimum.
' ,' ~
With ~his object in view, the invention relates -to a process for the production of an anion exchanger, particularly -for the treat-ment oF waste wa-ter, which is characterized in that cellulose or a cel-lulose derivative is treated with polyethylene imine in an aqueous re-action medium at a pH-value of 2-6, and the ion exchanger is recover-ed from the reaction mixture.
The recovery of the ion exchan0er from the reaction mix-ture can take place by decanting, filtering and other separating me-thods, and after having been separated from the reaction medium the ion exchanger can be washed and/or dried. It is, however, preferable to bring ~he ion exchanger on the market without first washing and drying it and to perform the washing with water only immediately be-fore it is taken into use.
The reaction of the cellulose or the cellulose derivative with the polyethylene imine can take place at ambient temperature, however, it is preferable, in order to reduce the reaction time and to increase the degree of reaction, to work at higher temperatures, e.g. in the range 40-90 C, preferably in the range 60-70 C.
The pH-value of the reaction mixture can advantageously be adjusted in the range from 4 to 5, which can be effected by means of an acid, preferably hydrochloric acid. The reaction time depends on the other reaction conditions, particularly whether stirring takes place or not. The reaction time is relatively long, usually in the range from two hours to four days.
The speed of reaction also depends on the concentration of the polyethylene imine solution. This concentration should therefore be at least 1% by weight, and preferably at least 2% by weight.
Solutions of 5-40% by weight are very suitable.
The polyethylene imine solution can be used successively ` 30 for several charges, seeing that upon removal from the first and also subsequent charges it still contains a sufficient amoun-t o-f polyethyle-ne imine for effecting additional reac-tions. Usually about 5-10% o-f the polyethylene imine is consumed in the production of the ion exchanger.
The reaction time is pre-ferably in the range from 1-4 days in order to obtain a very good activation of the material and to bind enough polyethylene to the cellulose or the cellulose derivatives.
As starting material it is preferred not to use pure cellulose, but a cellulose derivative. Some particular cellulose derivatives give an increased activity. One of the cellulose derivatives that may be ' .
3~i used with advantage is sulphonated lignocellulose, which is e.g. known as an intermediary product in the manufacturing of cellulose. Another preferred start-ing material is a mixture of cellu]ose derivatives, which is obtained from bark when this is treated in separate steps with alkali hydroxide solution and with sulphuric acid.
The compounds contained in this starting material are not de~ined.
However, it is evident that they contain sulphurous strongly acid groups, such as acidic sulphate ester groups or sulphonic acid groups as well as carboxyl groups and hydroxyl groups.
This starting material can advantageously be produced by first treat-ing comminuted bark preferably having an average particle size from .5-5 mm, pre-ferably from 1 to 3 mm, with an alkali hydroxide solution of at least 5% by weight, preferably 20-40% by weight, preferably sodium hydroxide solution, then washing with water, preferably to a pH-value of 9 or below, thereafter treating the bark with sulphuric acid of 30-75% by weight, preferably 40-70 and more pre-ferably 50-65%, and finally washing with water preferably up to a pH-value above 4. The time of treatment with the alkali hydroxide solution is .5-20, prefer-ably 3-10 hours, and the time of treatment with sulphuric acid is .5-8, prefer-ably 1-6 hours.
Especially for the use in the treatment of waste water, it is advant-ageous to mix the anion exchanger obtained by the reaction of polyethylene imine with activated clay, preferably A1203, in the ratio from 2:1 to 1:4~ preferably 1:2. The last mentioned value particularly applies to the use of the mixture for the purification of municipal waste water. The clay can advantageously be activated by treatment with nitric acid, but also clays otherwise activated can be used.
The ion exchanger according to the invention has a surprisingly high 63~735 efficiency in the treatment of waste water, and in particular it has a high selectivity towards proteins, polypeptides, amino acids, dyestuffs, humic acid, inorganic anions such as chromate ions or phosphate ions, and other impurities occurring in household or industrial waste water. E.g. this ion exchange can be used for the purification of municipal waste water and waste water from textile dyeing plants, galvanizing plants, slaughterhouses and fish filletting factories and also from the canning industry and soy bean factories.
The anion exchanger according to the invention can also be used for the recirculation of fish farm water when it is mixed with a : -~a-.
~6~735 cellulose cation exchanger and activated clay, such as clinoptilolite in the ratio 2:2:1 to 1:1:4. Since clinoptilolite is capable of removing ammonium a complete removal of nitrogen compounds in fish farm waters is obtained by using this mixture.
The anion exchanger according to the invention can in case of need easily be regenera-ted, e.g. by elution wi-th sodium hydroxide or an aqueous solution containing a mixture o-f sodium hydroxide and sodium chloride preferabiy a solution oF .1-1.5 M NaOH and 0.5-2 M
NaCI is used for the regeneration. After the regenera-tion a reac-tivation can, if necessary, be effected by treatment with polyethylene imine .
EXAMPLE .
As a starting material was used a cellulose derivative mix-ture produced in the following manner.
Pine bark was comminuted by means of a cutting machine to a particle size of .5-3 mm. The comminuted bark was placed in a ves-sel and covered with a 15% sodium hydroxide solution for seven hours.
After removal of the sodium hydroxide the bark was washed with wa-ter until the pH-value was 9 or below. Thereafter the bark was co-vered in the same vessel or another with 65% sulphuric acid for four hours. The bark was then washed until the pH-value was 4 or above.
An aqueous polyethylene imine solution of approximately 7%
was adjusted to pH 4.5 with hydrochloric acid. The starting material produced as described above was covered with this solution, the re-action mixture was heated for four hours to 70 C and was then left to stand for three days at ambient temperature. Thereafter the pro-duct of the process was separated by filtration, and the filtrate could be used for a further charge after making up for the consumed poly-ethylene imine solution and readjustment of the pH-value.
Immediately before use the moist ion exchanger produced as above described was washed several times with water. For determining the coefficient of selectivity solutions of azodyestuffs, dodecylbenzene sulphonic acid (DBS), humic acid, and potasium chromate were pro-duced and passed through a column of the anion exchanger. A glass column filled wi-th the anion exchanger having a diameter of 2.5 cm was used, the thickness of the bed was about 30 cm and the flow rate was 15 m per hour. The outflow frorn the ion exchanger column was analyzed for every 500 ml. The coefficient of selectivity determined by this analysis means the quantity of a substance which is taken up '73~
in preference to sodium chloride when the ionexchanger is treated with a solution, the dissolved matter of which comprises 50% of the substance in question and 5~6 sodium chloride. The coefficient of selectivity determined for the various subs-tances are shown in Table 1.
TAeLE 1.
25 mgll of solution pH of -the solution Selectivity coeFficien-t Red Azodyestuf-f 6.8-7.2 67 Yellow Azodyestuff 6.8-7.2 35 DBS 6.8-7.2 50 Humic acid 6.0-6.5 100 CrO4 6.5-6.8 19 In another test the anion exchanger produced as described 15 above was mixed with activated clay in a proportion such that the mixture consisted of 2/3 activated Al2O3 and 1/3 ionexchanger. This mixture was used for testing the removal of phosphorous from an aqueous solution. The mixture was -filled in-to a pilo-t plant having a diameter of 15 cm and a height of 2 m, a 1 m layer of the mixed 20 ionexchanger material being used. The activated Al2O3 is capable of removing orthophosphate, while the anion exchanger is capable of removing polyphosphate and organic phosphates. A flow rate of 10 bed volumes per hour was used corresponding to 175 I waste water per hour. The flow o-f waste water was directed upwards through the 25 column. After the column was saturated, it was regenerated by wash-ing with 35 I water, elution with 25 1 .5 M NaOH, and washing with 70 I water.
The following types of waste material were treated in the pi lot plant:
30 I. Waste water effluent from a biological filter, total phos-phorous content 9.6 mg/l.
I l . Waste water effluent from chemical precipi-tation, total phosphorous conten-t 0.61 mg/l.
I l l . Overflow from a rain water bassin, total phosphorous content 1.08 mg/l.
The column and the elution liquid were used four times be-fore the test here considered was carried out. Samples of the output were analyzed every second hour. The results are shown in the fol-Iowing Tables 2 and 3.
. 6 TABLE 2.
Capacity Sludge InflowBed volurnes m3 * I l/m3 was-te wa-ter.
I ......... 320 5, 5 5 0 . g0 Il......... 2200 38,4 5 0.13 Ill........ 1811 31,6 5 0.16 * 0.1 m3 is deducted corresponding 0.1 m3 washing water.
TABLE 3.
Soluble Sample soluble poly-(average) P total P soluble Ortho-P org. P phosphates Inflow I 9.6 7.3 6.1 0.7 0-5 Outflow 1 0. 95 0. 950. 57 0 . 2 0 . 2 Inflow l l 0.610.37 0.25 0.05 0.05 Outflow ll 0.060.06 0.01 0.03 0.02 Inflow lll 1.080.51 0.38 0.'11 0.04 Outflow lll 0.100.10 0.03 0.03 0.04 Tables 2 and 3 show that the capacity corresponds to about 90%
removal of phosphorus.
.
' , ' ~ ` ,,
The treatment of municipal and industrial waste water is be-5 coming an increasing problem, especially in industrialized countries.It is therefore technologically important to develop processes which give a high efficiency at relative low cost for the treatment of waste water which besides protein and heavy metals contains refractory components. Proteins can be treated on biological units, but often the 10 materials are so valuable that it would be natural to consider a reco-very process.
Proteins, polypeptides and amino acids can be removed by chemical precipitation. As precipitants are used lignin sulphuric acid and dodecylbenzene sulphonic acid, and others.
However, only very high molecular weight proteins are pre-cipitated and compounds such as proteins with medium and lower molecular weight, polypeptides and amino acids are not removed by this process.
It would therefore be desirable to have an ion exchanger 20 available which can remove such compounds and can therefore be used for the treatment of waste water, which has been subjected to the precipitation treatment. Examples of waste water for which such a combined treatment may be advantageous is such from fish filletting factories, dairies, slaughterhouses and other food processing plants.
25 This removal is furthermore of interest for the recirculation of water in fish farms.
A number of cellulose ion exchangers are already on the market. Examples are cellulose sulphate esters produced by reacting cellulose with SO3, and also cellulose phosphate esters. These are 30 capable of solving the above mentioned problem, but all these ion exchangers are prohibitively expensive.
It is the object of the invention to provide a process for the production of ion exchangers which have high efficiency in -the treatment of waste water and can be produced at the lowest possible 35 cost. Particularly, these ion exchangers should be capable of removing anionic organic compounds as well as pro-teins and other nitrogen compounds from the waste water. Moreover, the ion exchanger should be capable of regeneration in order to reduce the problem of disposing of consumed ion exchanger material to a minimum.
' ,' ~
With ~his object in view, the invention relates -to a process for the production of an anion exchanger, particularly -for the treat-ment oF waste wa-ter, which is characterized in that cellulose or a cel-lulose derivative is treated with polyethylene imine in an aqueous re-action medium at a pH-value of 2-6, and the ion exchanger is recover-ed from the reaction mixture.
The recovery of the ion exchan0er from the reaction mix-ture can take place by decanting, filtering and other separating me-thods, and after having been separated from the reaction medium the ion exchanger can be washed and/or dried. It is, however, preferable to bring ~he ion exchanger on the market without first washing and drying it and to perform the washing with water only immediately be-fore it is taken into use.
The reaction of the cellulose or the cellulose derivative with the polyethylene imine can take place at ambient temperature, however, it is preferable, in order to reduce the reaction time and to increase the degree of reaction, to work at higher temperatures, e.g. in the range 40-90 C, preferably in the range 60-70 C.
The pH-value of the reaction mixture can advantageously be adjusted in the range from 4 to 5, which can be effected by means of an acid, preferably hydrochloric acid. The reaction time depends on the other reaction conditions, particularly whether stirring takes place or not. The reaction time is relatively long, usually in the range from two hours to four days.
The speed of reaction also depends on the concentration of the polyethylene imine solution. This concentration should therefore be at least 1% by weight, and preferably at least 2% by weight.
Solutions of 5-40% by weight are very suitable.
The polyethylene imine solution can be used successively ` 30 for several charges, seeing that upon removal from the first and also subsequent charges it still contains a sufficient amoun-t o-f polyethyle-ne imine for effecting additional reac-tions. Usually about 5-10% o-f the polyethylene imine is consumed in the production of the ion exchanger.
The reaction time is pre-ferably in the range from 1-4 days in order to obtain a very good activation of the material and to bind enough polyethylene to the cellulose or the cellulose derivatives.
As starting material it is preferred not to use pure cellulose, but a cellulose derivative. Some particular cellulose derivatives give an increased activity. One of the cellulose derivatives that may be ' .
3~i used with advantage is sulphonated lignocellulose, which is e.g. known as an intermediary product in the manufacturing of cellulose. Another preferred start-ing material is a mixture of cellu]ose derivatives, which is obtained from bark when this is treated in separate steps with alkali hydroxide solution and with sulphuric acid.
The compounds contained in this starting material are not de~ined.
However, it is evident that they contain sulphurous strongly acid groups, such as acidic sulphate ester groups or sulphonic acid groups as well as carboxyl groups and hydroxyl groups.
This starting material can advantageously be produced by first treat-ing comminuted bark preferably having an average particle size from .5-5 mm, pre-ferably from 1 to 3 mm, with an alkali hydroxide solution of at least 5% by weight, preferably 20-40% by weight, preferably sodium hydroxide solution, then washing with water, preferably to a pH-value of 9 or below, thereafter treating the bark with sulphuric acid of 30-75% by weight, preferably 40-70 and more pre-ferably 50-65%, and finally washing with water preferably up to a pH-value above 4. The time of treatment with the alkali hydroxide solution is .5-20, prefer-ably 3-10 hours, and the time of treatment with sulphuric acid is .5-8, prefer-ably 1-6 hours.
Especially for the use in the treatment of waste water, it is advant-ageous to mix the anion exchanger obtained by the reaction of polyethylene imine with activated clay, preferably A1203, in the ratio from 2:1 to 1:4~ preferably 1:2. The last mentioned value particularly applies to the use of the mixture for the purification of municipal waste water. The clay can advantageously be activated by treatment with nitric acid, but also clays otherwise activated can be used.
The ion exchanger according to the invention has a surprisingly high 63~735 efficiency in the treatment of waste water, and in particular it has a high selectivity towards proteins, polypeptides, amino acids, dyestuffs, humic acid, inorganic anions such as chromate ions or phosphate ions, and other impurities occurring in household or industrial waste water. E.g. this ion exchange can be used for the purification of municipal waste water and waste water from textile dyeing plants, galvanizing plants, slaughterhouses and fish filletting factories and also from the canning industry and soy bean factories.
The anion exchanger according to the invention can also be used for the recirculation of fish farm water when it is mixed with a : -~a-.
~6~735 cellulose cation exchanger and activated clay, such as clinoptilolite in the ratio 2:2:1 to 1:1:4. Since clinoptilolite is capable of removing ammonium a complete removal of nitrogen compounds in fish farm waters is obtained by using this mixture.
The anion exchanger according to the invention can in case of need easily be regenera-ted, e.g. by elution wi-th sodium hydroxide or an aqueous solution containing a mixture o-f sodium hydroxide and sodium chloride preferabiy a solution oF .1-1.5 M NaOH and 0.5-2 M
NaCI is used for the regeneration. After the regenera-tion a reac-tivation can, if necessary, be effected by treatment with polyethylene imine .
EXAMPLE .
As a starting material was used a cellulose derivative mix-ture produced in the following manner.
Pine bark was comminuted by means of a cutting machine to a particle size of .5-3 mm. The comminuted bark was placed in a ves-sel and covered with a 15% sodium hydroxide solution for seven hours.
After removal of the sodium hydroxide the bark was washed with wa-ter until the pH-value was 9 or below. Thereafter the bark was co-vered in the same vessel or another with 65% sulphuric acid for four hours. The bark was then washed until the pH-value was 4 or above.
An aqueous polyethylene imine solution of approximately 7%
was adjusted to pH 4.5 with hydrochloric acid. The starting material produced as described above was covered with this solution, the re-action mixture was heated for four hours to 70 C and was then left to stand for three days at ambient temperature. Thereafter the pro-duct of the process was separated by filtration, and the filtrate could be used for a further charge after making up for the consumed poly-ethylene imine solution and readjustment of the pH-value.
Immediately before use the moist ion exchanger produced as above described was washed several times with water. For determining the coefficient of selectivity solutions of azodyestuffs, dodecylbenzene sulphonic acid (DBS), humic acid, and potasium chromate were pro-duced and passed through a column of the anion exchanger. A glass column filled wi-th the anion exchanger having a diameter of 2.5 cm was used, the thickness of the bed was about 30 cm and the flow rate was 15 m per hour. The outflow frorn the ion exchanger column was analyzed for every 500 ml. The coefficient of selectivity determined by this analysis means the quantity of a substance which is taken up '73~
in preference to sodium chloride when the ionexchanger is treated with a solution, the dissolved matter of which comprises 50% of the substance in question and 5~6 sodium chloride. The coefficient of selectivity determined for the various subs-tances are shown in Table 1.
TAeLE 1.
25 mgll of solution pH of -the solution Selectivity coeFficien-t Red Azodyestuf-f 6.8-7.2 67 Yellow Azodyestuff 6.8-7.2 35 DBS 6.8-7.2 50 Humic acid 6.0-6.5 100 CrO4 6.5-6.8 19 In another test the anion exchanger produced as described 15 above was mixed with activated clay in a proportion such that the mixture consisted of 2/3 activated Al2O3 and 1/3 ionexchanger. This mixture was used for testing the removal of phosphorous from an aqueous solution. The mixture was -filled in-to a pilo-t plant having a diameter of 15 cm and a height of 2 m, a 1 m layer of the mixed 20 ionexchanger material being used. The activated Al2O3 is capable of removing orthophosphate, while the anion exchanger is capable of removing polyphosphate and organic phosphates. A flow rate of 10 bed volumes per hour was used corresponding to 175 I waste water per hour. The flow o-f waste water was directed upwards through the 25 column. After the column was saturated, it was regenerated by wash-ing with 35 I water, elution with 25 1 .5 M NaOH, and washing with 70 I water.
The following types of waste material were treated in the pi lot plant:
30 I. Waste water effluent from a biological filter, total phos-phorous content 9.6 mg/l.
I l . Waste water effluent from chemical precipi-tation, total phosphorous conten-t 0.61 mg/l.
I l l . Overflow from a rain water bassin, total phosphorous content 1.08 mg/l.
The column and the elution liquid were used four times be-fore the test here considered was carried out. Samples of the output were analyzed every second hour. The results are shown in the fol-Iowing Tables 2 and 3.
. 6 TABLE 2.
Capacity Sludge InflowBed volurnes m3 * I l/m3 was-te wa-ter.
I ......... 320 5, 5 5 0 . g0 Il......... 2200 38,4 5 0.13 Ill........ 1811 31,6 5 0.16 * 0.1 m3 is deducted corresponding 0.1 m3 washing water.
TABLE 3.
Soluble Sample soluble poly-(average) P total P soluble Ortho-P org. P phosphates Inflow I 9.6 7.3 6.1 0.7 0-5 Outflow 1 0. 95 0. 950. 57 0 . 2 0 . 2 Inflow l l 0.610.37 0.25 0.05 0.05 Outflow ll 0.060.06 0.01 0.03 0.02 Inflow lll 1.080.51 0.38 0.'11 0.04 Outflow lll 0.100.10 0.03 0.03 0.04 Tables 2 and 3 show that the capacity corresponds to about 90%
removal of phosphorus.
.
' , ' ~ ` ,,
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of an anion exchanger, wherein cellulose or a cellulose derivative is treated with polyethylene imine in an aqueous reaction medium at a pH-value of 2-6, and the ion exchanger is recovered from the reaction mixture.
2. A process as in claim 1, wherein the reaction is carried out at a temperature of 40-90°C.
3. A process as in claim 1, wherein the reaction is carried out at a pH-value of 4-5.
4. A process as in claim 1, wherein the reaction time is within the range from two hours to four days.
5. A process as in claim 1, wherein a polyethylene imine solution of a concentration of at least 1% is used.
6. A process as in claim 1, wherein sulphonated lignocellulose is used as the cellulose derivative.
7. A process as in claim 1, using a cellulose derivative obtained by treating a cellulose material in separate steps with alkali hydroxide and with sulphuric acid.
8. A process as in claim 7, wherein bark is used as the starting cellulose material.
9. The use of an ion exchanger produced according to claim 1 for the treatment of waste water.
10. The use of an ion exchanger as in claim 9, the ion exchanger being mixed with activated clay in a ratio from 2:1 to 1:4.
11. A process as in claim 1, wherein the reaction is carried out at a temperature of 60-70°C.
12. A process as in claim 3 which uses hydrochloric acid for the adjustment of the pH-value.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000393124A CA1169735A (en) | 1981-12-23 | 1981-12-23 | Process for the production of an anion exchanger, and a use of same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA000393124A CA1169735A (en) | 1981-12-23 | 1981-12-23 | Process for the production of an anion exchanger, and a use of same |
Publications (1)
Publication Number | Publication Date |
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CA1169735A true CA1169735A (en) | 1984-06-26 |
Family
ID=4121694
Family Applications (1)
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CA000393124A Expired CA1169735A (en) | 1981-12-23 | 1981-12-23 | Process for the production of an anion exchanger, and a use of same |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5073272A (en) * | 1988-11-15 | 1991-12-17 | Aluminum Company Of America | Method for using a flocculant powder |
-
1981
- 1981-12-23 CA CA000393124A patent/CA1169735A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5073272A (en) * | 1988-11-15 | 1991-12-17 | Aluminum Company Of America | Method for using a flocculant powder |
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