CA1143359A - Oil-containing waste water treating material consisting of modified active carbon - Google Patents
Oil-containing waste water treating material consisting of modified active carbonInfo
- Publication number
- CA1143359A CA1143359A CA000357402A CA357402A CA1143359A CA 1143359 A CA1143359 A CA 1143359A CA 000357402 A CA000357402 A CA 000357402A CA 357402 A CA357402 A CA 357402A CA 1143359 A CA1143359 A CA 1143359A
- Authority
- CA
- Canada
- Prior art keywords
- active carbon
- oil
- waste water
- vinyl compound
- treating material
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- 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
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/681—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of solid materials for removing an oily layer on water
Abstract
ABSTRACT OF THE DISCLOSURE
An oil-containing waste water treating material, comprising an active carbon upon whose surface is chemically bonded at least one nitrogenous compound which is an amine or a quaternarized derivative thereof.
An oil-containing waste water treating material, comprising an active carbon upon whose surface is chemically bonded at least one nitrogenous compound which is an amine or a quaternarized derivative thereof.
Description
~143359 OIL-CONTAINING WASTE WAT-ER TREATING MATERIAL
CONSISTING OF MODIFIED ACTIV CARBON
BACKGROUND OF THE INVENTION
Field of the Invention: -The present invention relates to an oil-containing waste water treating material which is effective in treating cleaning oil fractioffs, sewage or factory waste water containing various oil fraction mixtures and solids.
Description of the Prior Art:
Many oil-water separating methods are known for the treatment of oil-containing waste water. For example, in one conventional technique applied to crude waste water which contains oil fractions comparatively easy to separate by a physical process, the waste water is filtered with sand to reduce the load on an active carbon adsorbent, is then passed through active carbon ta adsorb oil thereon and is drained~
If further processing is desirable, the waste water, after filtration over the sand bed and before contact with active carbon, is charged into a tower containing synthetic fibers having an affinity for oil, and the water discharged from the tower is then sent to the active carbon filtration zone. However, because of recent, more str~ngent regulations concerning the dralni~g of waste water, the convent~onal active carbon treatment processes are insufflcient in removing oil fractions~from waste water to the required degree, and there~ore, higher levels of treatment of waste water are required. This need is heightened by the fact that clean water itself is a valuable resource and therefore with efficient purification, waste water can serve as a .
.. ~ . ~ ,, -.. , : . , . . . ~ :
,' ~ . . , , - .. ~ ~ ' 1~3359 source for pure water. On the other hand~ in the instances of waste waters containing oil fractions which are difficult to remove such as those containing emulsified oil, a method is needed by which oil can be removed with a high degree of effectiveness. Therefore, a need continues to exist for an improved technique of removing contaminating oil fractions from various types of waste waters.
SUMMARY OF THE INVENTION
Accordingly, one objec~ of the present invention is to provide an adsorbent material for the treatment of oil-containing waste water which removes the oil fraction with substant;al efficiency.
Briefly, this object and other objects of the present invention as hereinafter will become more readily apparent can be attained by an oil-containing waste water treating material comprising an active carbon upon whose surface is chemically bonded at least one nitrogenous compound which is an amine or a quaternarized derivative thereof.
DESCRIPTION OF T~E PREFERRED EMBODIMENTS
In the preparation of the modified active carbon adsorbent of the present invention, the active carbon which is used is preferably ; a granular or finely powdered material having a large surface area.
20With regard to the nitrogenous compounds which are to be chemically bonded onto the surface of the active carbon, suitable compounds include primary amine compounds such as isopropylamine, isoprQpanolamine, N-aminoethylethanolamine, N-aminoprQpylmorpholine, ,~
'' ..' ~ :' - ' -.
~3359
CONSISTING OF MODIFIED ACTIV CARBON
BACKGROUND OF THE INVENTION
Field of the Invention: -The present invention relates to an oil-containing waste water treating material which is effective in treating cleaning oil fractioffs, sewage or factory waste water containing various oil fraction mixtures and solids.
Description of the Prior Art:
Many oil-water separating methods are known for the treatment of oil-containing waste water. For example, in one conventional technique applied to crude waste water which contains oil fractions comparatively easy to separate by a physical process, the waste water is filtered with sand to reduce the load on an active carbon adsorbent, is then passed through active carbon ta adsorb oil thereon and is drained~
If further processing is desirable, the waste water, after filtration over the sand bed and before contact with active carbon, is charged into a tower containing synthetic fibers having an affinity for oil, and the water discharged from the tower is then sent to the active carbon filtration zone. However, because of recent, more str~ngent regulations concerning the dralni~g of waste water, the convent~onal active carbon treatment processes are insufflcient in removing oil fractions~from waste water to the required degree, and there~ore, higher levels of treatment of waste water are required. This need is heightened by the fact that clean water itself is a valuable resource and therefore with efficient purification, waste water can serve as a .
.. ~ . ~ ,, -.. , : . , . . . ~ :
,' ~ . . , , - .. ~ ~ ' 1~3359 source for pure water. On the other hand~ in the instances of waste waters containing oil fractions which are difficult to remove such as those containing emulsified oil, a method is needed by which oil can be removed with a high degree of effectiveness. Therefore, a need continues to exist for an improved technique of removing contaminating oil fractions from various types of waste waters.
SUMMARY OF THE INVENTION
Accordingly, one objec~ of the present invention is to provide an adsorbent material for the treatment of oil-containing waste water which removes the oil fraction with substant;al efficiency.
Briefly, this object and other objects of the present invention as hereinafter will become more readily apparent can be attained by an oil-containing waste water treating material comprising an active carbon upon whose surface is chemically bonded at least one nitrogenous compound which is an amine or a quaternarized derivative thereof.
DESCRIPTION OF T~E PREFERRED EMBODIMENTS
In the preparation of the modified active carbon adsorbent of the present invention, the active carbon which is used is preferably ; a granular or finely powdered material having a large surface area.
20With regard to the nitrogenous compounds which are to be chemically bonded onto the surface of the active carbon, suitable compounds include primary amine compounds such as isopropylamine, isoprQpanolamine, N-aminoethylethanolamine, N-aminoprQpylmorpholine, ,~
'' ..' ~ :' - ' -.
~3359
2-ethylhexylamine and the like; secondary amine compounds such as diethylamine, di-n-butylamine and the like; tertiary amine compounds such as trime~hylamine, dimethylethanolamine, triethanolamine and methyldiethanolamine and the like; polyethylenepolyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; nitrogenous vinyl compounds having amine structures such as dimethylaminoethyl methacrylate, diethylamino-ethyl methacrylate and dimethylacrylamide; nitrogenous vinyl compounds having quaternary ammonium structures such as 2-hydroxy-
3-methacryloxypropyltrimethylammonium chloride, methacrylic acid dimethylaminoethylmethyl chloride and the likei and nitrogenous vinyl compounds having pyridine structures such as 2-vinylpyridine and 4-vinylpyridine. Preferred nitrogenous compounds for the ~nodification of active carbon are selected from this graup of compounds.
The modified active carbon of the present invention can be prepared by a variety of methods. In one method a halogen such as fluorine, chlorine, bromine or iodlne is bonded to the surface of active carbon havlng a phenanthrene structure, and then the halogenated active carbon is heated in an aqueous solutlon of a primary or secondary amine compound or a polyethylenepolyamine, whereby the halogen atoms are replaced by the amine compound to prepare the modified active carbon.
In another technique the halogenated active carbon immediate prepared as described above can be heated ~n an aqueous solution of a tertiary amine compound which results in modification of the active :,: , ` ' , `. ~
:
.
119~3359 carbon surface to a quaternary ammonium salt.
The quaternary ammonium salt modification can also be prepared by heating the tertiary amine compound modified active carbon obtained in the first method discussed above in a proper solvent such as nitromethane together with a halide compound such as hydrochloric acid, methyl iodide, methyl chloride or butyl bromide.
In yet another method of preparation, a nitrogenous vinyl compound having an amine structure,which includes a pyridine structure, or a tertiary ammonium structure, is graft-polymerized onto the surface of active carbon to modify it. Thereafter, if desired, the modified carbon can be treated by a halide compound to quaternarize the amine structure. For example, in order to graft-polymerize a nitrogenous vinyl compound having a tertiary amine structure or quaternary ammonium structure, the nitrogenous vinyl compound is dissolved in a proper solvent such as an alcohol of which methanol is exemplary, and the polymerization reaction is promoted with an initiator such as azobisisobutyronitrile to graft-polymerize the nitrogenous vinyl compound onto the surface of actlve carbon.
Thereafter, if desired, the active carbon modified with the nitro-; 20 genous vinyl compound having an amine structure can be treated wlth a~hali~e compound in a proper solvent such as methanol in order to convert the amine structure to the quaternary salt.
Fuither, if desired, a nitrogenous vinyl campound having an amine structure can be added to the modified carbon Z5 and thereafter again treated with a halide compound to r ,, ~
.
.' ' ~ . . . ' ' ~ .
11~3359 quaternarize the added nitrogenous vinyl compound.
The treating material of the present invention which consists of active carbon modified by a nitrogenous compound as described above is far superior to conventional actlve carbon materials ~hose surfaces have not been modified in the removal of oil fractions from waste water. Further, in the cases where the nitrogenous compound introduced onto the surface of the act;ve carbon is a polar or ion-exchanging compound, the modified active carbon will exhibit such a high degree o~ water affinity that it is very easily handled in waste water when charged into a column and when used as a slurry.
The modified active carbon treating material of the present invention can be used to clean waste water containing single or mixed oil fractions consisting of various mineral oils and animal and vegetable oils and can remove the o~l fractions even if they are dispersed or emulsified in the waste water. Further, even if solids or pollutants other than oil fractjons are contained in the waste water, the treating capacity wlll not be adversely affected. Moreover, because the nitrogenous compound used for the modification of the active carbon is chemically bonded to the active carbon, there is no poss1bility at all of secondary p,ollution by outflow into the water to be treated.
The active carbon treating material of the present invention can be used not only as an adsorbing material, but also as a grain coarsening material. When it is to be used as an adsorbing material, a slurry adsorbing system can be adopted. Usually, however, it is A
:
. : ' ~3359 preferable to use a charged tower adsorbing system. When the modified active carbon is to be used as a grain coarsening material, the charged tower system can also be used, but a cartridge is convenient to handle.
The active carbon treating material of the present invention when used as an adsorbing material or grain coarsening material by the charged tower system can be reactivated for use by reverse flow washing or surface washing. When washing the material, water or air can be used.
The active carbon treating material of the present invention is very effective in *reating waste water of widely varying types including such emulsified oil waste waters as cutting oil waste water, rolling oil waste water, oil tank washing waste water, machine washing waste water, paint factory waste water, food factory waste water and compressor drainage and such dispersed oils as oil tanker ballast water and bilge water which have been considered to be very difficult to treat.
Thus, broadly, the invention contemplates an oil-containing waste water treating material, which comprises an active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound which has at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
.
1~3359 The invention also encompasses the novel method of removal of oil fractions from oil-containing waste water which comprises contacting the waste water with a bed of active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound having at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.
In a four-necked flask, 900 g of carbon tetra-chloride was added to 400 g of unmodified granular active carbon while being stirred.
,,.~,, - ~ - ~
` 114~359 The mixture WdS refluxed at 100C and thereafter 30 9 of bromine was gradually added thereto through a dropping funnel. The mixture was reacted for 8 hours. After the reaction, the active carbon was well washed with carbon tetrachloride to remove unreacted bromine and was then air-dried until there was no bromine. Upon elemental analysis, components other than C (carbon), H (hydrogen) and N (nitrogen) had greatly increased and were present in amounts of about 40% as compared with unmodified active carbon. It was clear that bromine had been introduced into the active carbon substrate.
H in % C in ~ N in X
by weight by weight by weight Bromine Not more 60.4 Not more Active Carbon than 0.3 than 0.3 UnmodifiedNot more 91.1 Not more Active Carbon than 0.3 than 0.3 In-a four-necked flask, 80 ml of an aqueous solution of 25~
diethylenetriamine was added to 4ao 9 of the bromine active carbon while being stirred, and the mixture was reacted under reflux at ~loooc for 8 hours. After the reaction, the active carbon was well washed wi~th distilled water to completely remove unreacted amine and was then air-dried. When an elemental analysis was conducted, 1.1%
N was present as compared to the unmodified active carbon. It was clear that diethylenetriamine had been introduced by the chemical .., 114335~ ' reaction. It is believed that the chemical reaction involved is as follows:
~CH2CH2NW2 ~CH2CH2NH2 AC~Br)n + n NH - ~ AC ~N )n + n HBr (AC: active carbon) H in % C in % N in ~, by weight by weight by weight Amino Not more 73.0 l.l Active Carbonthan 0.8 -A column of an ;nside diameter of 20 mm was charged with the diethylenetriamine modified granular active carbon to a height of 40 cm at a charging density of 0.79 g/cm3. A model emulsified oil containing lO0 ppm of turbine oil and 5 ppm of a non-ionic surface active agent and stirred for lO minutes with a domestic mixer as a crude water to be treated was passed through this charged layer at a rate of l m/hr.
The o~il fraction concentrations of the crude water and treated water were measured by measuring the turbid;ty of water samples. The crude ~water was found to have a turbidity of 80 to 120 ppm, while the treated water had a turbidity of 20 to 30 ppm. Even when the water passed over the adsorbent for 50 hours, these values did not substantially :: ~ : : :
~ fluctuate.
....
~143359 -- 1o When a column was charged with unmodified granular active carbon in the same manner as described in Example 1 and a model emulsified oil was passed through the column to test the oil fraction removal S ability of the carbon, it was found that treated water had a turbidity of over 30 ppm after 10 hours of processing time but that with increasing time the turbidity of the treated water increased.
The crude water entering the column had a turbidity of ~0 to l20 ppm.
It is apparent from these results that the performance of the unmodified active carbon was inferior to the modified active carbon material of the present invention.
In a four-necked flask, 2-vinylpyridine/methanol ~50 g/ZOO ml) was added to 50 9 of unmodified granular active carbon while being , 15 stirred, and the mixture was reacted under reflux at 64C for 3 hours by using azobisisobutyronitrile as a polymerization initiator under a flow of nitrogen gas. After the reaction, the active carbon was well washed with methanol to completely remove 2-vinylpyridine and was then air-dried. Upon elemental analysis, it was found that 1.8~ N
20 ~ was present in comparison to the unmodified active carbon whi-ch has a N content of essentially zero. It was clear that 2-vinylpyridine had been introduced into the carbon by graft polymerization. The chemical reaction involved is believed to be as follows:
~;,i .
.
' .
~43359 AC + n CH=CH2 ~ AC ~CH-CH2~ n N
H in % C in % N in ~
by weight by weight by weight 52-Vinylpyridine Grafted on 1.0 90.2 1.8 Active Carbon In a four-necked flask, a solution of n-butyl bromide/nitro-methane (5 9/300 ml) was added to 9 9 of the 2-vinylpyridine grafted active carbon contained in Example 2 while being stirred, and the mixture was reacted under reflux at 97C for 8 hours. After the reaction, the active carbon was well washed with nitromethane to :
; completely remove the unreacted n-butyl bromide and was then air-., ~ dried. Upon elemental analysis, components other than C, H and N had increased~by an amount of 13% in comparison to unmodified active carbon, and the quantity of nitrogen was 2.6~ Therefore, it was clear that n-butyl bromide had been introducéd into the active carbon and that the nitrogen of the 2-vinylpyridine had been quaternarized.
The chemical reaction involved is believed to be as follows:
AC ~CH CH2~ n ~ n CH3CH2CH2CH2Br --~AC ~CH-CH2~
CHz zC zCH3 , .
, .
~: : -.
, ~ ~-, . . ~ . . . ~
~143359 -H in ~ C in ~ N in %
by weight by weight by weight Quaternary 2-vinylpyridine 1.1 83.0 2.6 Grafted onto Active Carbon In a four-necked flask, a solution of 2-hydroxy-3-methacryloxy-propyltrimethylammonium chloride (A)/ethanol (50 9/200 ml) was added to 50 9 of unmodified active carbon while being stirred, and the mixture was reacted under reflux at 78C for 3 hours using azobisiso-butyronitrile as an initiator under a flow of nitrogen gas. After the reaction, the active carbon was well washed with ethanol to completely remove unreacted (A) material and was then air-dried.
Upon elemental analysisi it was found that the modified carbon material ; ~ contained 0.7 % N in comparison to essentially zero percent nitrogen for unmodified active carbon. It was clear that (A) had been ;introduced into the carbon by graft polymerization. The chemical reaction involved is believed to be as follows:
20~ , ~ CH3 AC * n CH2 = C CH
COCH2CHCH2 @3 N - CH~Cl ~3 .
' ~1~3359 . - l3 -AC ~CH2- C ~~n CH
COCH2CHCH2 63 N - CH3Cl Q
-H in % C in ~ N in %
by weightby weight by ~eight -(A) Grafted onto 1.1 85.7 0.7 Active Carbon
The modified active carbon of the present invention can be prepared by a variety of methods. In one method a halogen such as fluorine, chlorine, bromine or iodlne is bonded to the surface of active carbon havlng a phenanthrene structure, and then the halogenated active carbon is heated in an aqueous solutlon of a primary or secondary amine compound or a polyethylenepolyamine, whereby the halogen atoms are replaced by the amine compound to prepare the modified active carbon.
In another technique the halogenated active carbon immediate prepared as described above can be heated ~n an aqueous solution of a tertiary amine compound which results in modification of the active :,: , ` ' , `. ~
:
.
119~3359 carbon surface to a quaternary ammonium salt.
The quaternary ammonium salt modification can also be prepared by heating the tertiary amine compound modified active carbon obtained in the first method discussed above in a proper solvent such as nitromethane together with a halide compound such as hydrochloric acid, methyl iodide, methyl chloride or butyl bromide.
In yet another method of preparation, a nitrogenous vinyl compound having an amine structure,which includes a pyridine structure, or a tertiary ammonium structure, is graft-polymerized onto the surface of active carbon to modify it. Thereafter, if desired, the modified carbon can be treated by a halide compound to quaternarize the amine structure. For example, in order to graft-polymerize a nitrogenous vinyl compound having a tertiary amine structure or quaternary ammonium structure, the nitrogenous vinyl compound is dissolved in a proper solvent such as an alcohol of which methanol is exemplary, and the polymerization reaction is promoted with an initiator such as azobisisobutyronitrile to graft-polymerize the nitrogenous vinyl compound onto the surface of actlve carbon.
Thereafter, if desired, the active carbon modified with the nitro-; 20 genous vinyl compound having an amine structure can be treated wlth a~hali~e compound in a proper solvent such as methanol in order to convert the amine structure to the quaternary salt.
Fuither, if desired, a nitrogenous vinyl campound having an amine structure can be added to the modified carbon Z5 and thereafter again treated with a halide compound to r ,, ~
.
.' ' ~ . . . ' ' ~ .
11~3359 quaternarize the added nitrogenous vinyl compound.
The treating material of the present invention which consists of active carbon modified by a nitrogenous compound as described above is far superior to conventional actlve carbon materials ~hose surfaces have not been modified in the removal of oil fractions from waste water. Further, in the cases where the nitrogenous compound introduced onto the surface of the act;ve carbon is a polar or ion-exchanging compound, the modified active carbon will exhibit such a high degree o~ water affinity that it is very easily handled in waste water when charged into a column and when used as a slurry.
The modified active carbon treating material of the present invention can be used to clean waste water containing single or mixed oil fractions consisting of various mineral oils and animal and vegetable oils and can remove the o~l fractions even if they are dispersed or emulsified in the waste water. Further, even if solids or pollutants other than oil fractjons are contained in the waste water, the treating capacity wlll not be adversely affected. Moreover, because the nitrogenous compound used for the modification of the active carbon is chemically bonded to the active carbon, there is no poss1bility at all of secondary p,ollution by outflow into the water to be treated.
The active carbon treating material of the present invention can be used not only as an adsorbing material, but also as a grain coarsening material. When it is to be used as an adsorbing material, a slurry adsorbing system can be adopted. Usually, however, it is A
:
. : ' ~3359 preferable to use a charged tower adsorbing system. When the modified active carbon is to be used as a grain coarsening material, the charged tower system can also be used, but a cartridge is convenient to handle.
The active carbon treating material of the present invention when used as an adsorbing material or grain coarsening material by the charged tower system can be reactivated for use by reverse flow washing or surface washing. When washing the material, water or air can be used.
The active carbon treating material of the present invention is very effective in *reating waste water of widely varying types including such emulsified oil waste waters as cutting oil waste water, rolling oil waste water, oil tank washing waste water, machine washing waste water, paint factory waste water, food factory waste water and compressor drainage and such dispersed oils as oil tanker ballast water and bilge water which have been considered to be very difficult to treat.
Thus, broadly, the invention contemplates an oil-containing waste water treating material, which comprises an active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound which has at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
.
1~3359 The invention also encompasses the novel method of removal of oil fractions from oil-containing waste water which comprises contacting the waste water with a bed of active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound having at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.
In a four-necked flask, 900 g of carbon tetra-chloride was added to 400 g of unmodified granular active carbon while being stirred.
,,.~,, - ~ - ~
` 114~359 The mixture WdS refluxed at 100C and thereafter 30 9 of bromine was gradually added thereto through a dropping funnel. The mixture was reacted for 8 hours. After the reaction, the active carbon was well washed with carbon tetrachloride to remove unreacted bromine and was then air-dried until there was no bromine. Upon elemental analysis, components other than C (carbon), H (hydrogen) and N (nitrogen) had greatly increased and were present in amounts of about 40% as compared with unmodified active carbon. It was clear that bromine had been introduced into the active carbon substrate.
H in % C in ~ N in X
by weight by weight by weight Bromine Not more 60.4 Not more Active Carbon than 0.3 than 0.3 UnmodifiedNot more 91.1 Not more Active Carbon than 0.3 than 0.3 In-a four-necked flask, 80 ml of an aqueous solution of 25~
diethylenetriamine was added to 4ao 9 of the bromine active carbon while being stirred, and the mixture was reacted under reflux at ~loooc for 8 hours. After the reaction, the active carbon was well washed wi~th distilled water to completely remove unreacted amine and was then air-dried. When an elemental analysis was conducted, 1.1%
N was present as compared to the unmodified active carbon. It was clear that diethylenetriamine had been introduced by the chemical .., 114335~ ' reaction. It is believed that the chemical reaction involved is as follows:
~CH2CH2NW2 ~CH2CH2NH2 AC~Br)n + n NH - ~ AC ~N )n + n HBr (AC: active carbon) H in % C in % N in ~, by weight by weight by weight Amino Not more 73.0 l.l Active Carbonthan 0.8 -A column of an ;nside diameter of 20 mm was charged with the diethylenetriamine modified granular active carbon to a height of 40 cm at a charging density of 0.79 g/cm3. A model emulsified oil containing lO0 ppm of turbine oil and 5 ppm of a non-ionic surface active agent and stirred for lO minutes with a domestic mixer as a crude water to be treated was passed through this charged layer at a rate of l m/hr.
The o~il fraction concentrations of the crude water and treated water were measured by measuring the turbid;ty of water samples. The crude ~water was found to have a turbidity of 80 to 120 ppm, while the treated water had a turbidity of 20 to 30 ppm. Even when the water passed over the adsorbent for 50 hours, these values did not substantially :: ~ : : :
~ fluctuate.
....
~143359 -- 1o When a column was charged with unmodified granular active carbon in the same manner as described in Example 1 and a model emulsified oil was passed through the column to test the oil fraction removal S ability of the carbon, it was found that treated water had a turbidity of over 30 ppm after 10 hours of processing time but that with increasing time the turbidity of the treated water increased.
The crude water entering the column had a turbidity of ~0 to l20 ppm.
It is apparent from these results that the performance of the unmodified active carbon was inferior to the modified active carbon material of the present invention.
In a four-necked flask, 2-vinylpyridine/methanol ~50 g/ZOO ml) was added to 50 9 of unmodified granular active carbon while being , 15 stirred, and the mixture was reacted under reflux at 64C for 3 hours by using azobisisobutyronitrile as a polymerization initiator under a flow of nitrogen gas. After the reaction, the active carbon was well washed with methanol to completely remove 2-vinylpyridine and was then air-dried. Upon elemental analysis, it was found that 1.8~ N
20 ~ was present in comparison to the unmodified active carbon whi-ch has a N content of essentially zero. It was clear that 2-vinylpyridine had been introduced into the carbon by graft polymerization. The chemical reaction involved is believed to be as follows:
~;,i .
.
' .
~43359 AC + n CH=CH2 ~ AC ~CH-CH2~ n N
H in % C in % N in ~
by weight by weight by weight 52-Vinylpyridine Grafted on 1.0 90.2 1.8 Active Carbon In a four-necked flask, a solution of n-butyl bromide/nitro-methane (5 9/300 ml) was added to 9 9 of the 2-vinylpyridine grafted active carbon contained in Example 2 while being stirred, and the mixture was reacted under reflux at 97C for 8 hours. After the reaction, the active carbon was well washed with nitromethane to :
; completely remove the unreacted n-butyl bromide and was then air-., ~ dried. Upon elemental analysis, components other than C, H and N had increased~by an amount of 13% in comparison to unmodified active carbon, and the quantity of nitrogen was 2.6~ Therefore, it was clear that n-butyl bromide had been introducéd into the active carbon and that the nitrogen of the 2-vinylpyridine had been quaternarized.
The chemical reaction involved is believed to be as follows:
AC ~CH CH2~ n ~ n CH3CH2CH2CH2Br --~AC ~CH-CH2~
CHz zC zCH3 , .
, .
~: : -.
, ~ ~-, . . ~ . . . ~
~143359 -H in ~ C in ~ N in %
by weight by weight by weight Quaternary 2-vinylpyridine 1.1 83.0 2.6 Grafted onto Active Carbon In a four-necked flask, a solution of 2-hydroxy-3-methacryloxy-propyltrimethylammonium chloride (A)/ethanol (50 9/200 ml) was added to 50 9 of unmodified active carbon while being stirred, and the mixture was reacted under reflux at 78C for 3 hours using azobisiso-butyronitrile as an initiator under a flow of nitrogen gas. After the reaction, the active carbon was well washed with ethanol to completely remove unreacted (A) material and was then air-dried.
Upon elemental analysisi it was found that the modified carbon material ; ~ contained 0.7 % N in comparison to essentially zero percent nitrogen for unmodified active carbon. It was clear that (A) had been ;introduced into the carbon by graft polymerization. The chemical reaction involved is believed to be as follows:
20~ , ~ CH3 AC * n CH2 = C CH
COCH2CHCH2 @3 N - CH~Cl ~3 .
' ~1~3359 . - l3 -AC ~CH2- C ~~n CH
COCH2CHCH2 63 N - CH3Cl Q
-H in % C in ~ N in %
by weightby weight by ~eight -(A) Grafted onto 1.1 85.7 0.7 Active Carbon
4-Vinylpyridine was used instead of the 2-vinylpyridine in Example 2 and was chemically bonded to granular active carbon by graft po1ymerizdtion. Thereafter, the nitrogen content ~as quaternarized by hydrochloric acid to obta;n a modified active carbon.
: The chemical reaction invol-ved 1s believed to be as follows:
AC + n CH = CH2 ~. AC ~CH-CH2~ n AC ~CH-CH2~ n + n HCl ~ AC ~CH-CH2~ n ; 20 H Cl ~?
: When a column was charged with the above-modified active carbon : ~ ~ in the same manner as described ;n Example l and a model emulsified .
' ~1~33S9 oil was passed through it to test the oil fraction removal ability of the modified carbon, it was found that the turbidity of the treated water was 20 ppm even after 200 hours of treatment. The crude water starting material had a turbidity of 80 to 120 ppm.
The quaternarized 4-vinylpyridine grafted active carbon obtained in Example 5 was further reacted with 4-vinylpyridine. The product obtained was then quaternarized once again with hydrochloric acid to obtain a modified active carbon material. The chemical reaction involved is believed to be as follows:
AC ~CH-CH2~ n ~ n CH = CH2 -~ AC ~CH-CH2~ n 'C10 H Cl ~3 CH2 ~ ~ 15 `~ ~' :: :
~` ~
, :
AC ~CH CH2~ n n HCl ~ AC ~CH-CH2~ n I ~ Cl (~) I ' C
CH2 C'~2 H Cl ~
When a column was charged with the above-modified active carbon in the same manner as described in Example 5 and a model emulsified oil was passed through it to test the oil fraction removal ability of the modified carbon, it was found that the treated water discharged had a turbidity of 15 ppm and this value was maintained even after ; ' ~ the passage of water for 25Q hours. The crude water starting material had a turbidity of 80 to 120 ppm.
15Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
: The chemical reaction invol-ved 1s believed to be as follows:
AC + n CH = CH2 ~. AC ~CH-CH2~ n AC ~CH-CH2~ n + n HCl ~ AC ~CH-CH2~ n ; 20 H Cl ~?
: When a column was charged with the above-modified active carbon : ~ ~ in the same manner as described ;n Example l and a model emulsified .
' ~1~33S9 oil was passed through it to test the oil fraction removal ability of the modified carbon, it was found that the turbidity of the treated water was 20 ppm even after 200 hours of treatment. The crude water starting material had a turbidity of 80 to 120 ppm.
The quaternarized 4-vinylpyridine grafted active carbon obtained in Example 5 was further reacted with 4-vinylpyridine. The product obtained was then quaternarized once again with hydrochloric acid to obtain a modified active carbon material. The chemical reaction involved is believed to be as follows:
AC ~CH-CH2~ n ~ n CH = CH2 -~ AC ~CH-CH2~ n 'C10 H Cl ~3 CH2 ~ ~ 15 `~ ~' :: :
~` ~
, :
AC ~CH CH2~ n n HCl ~ AC ~CH-CH2~ n I ~ Cl (~) I ' C
CH2 C'~2 H Cl ~
When a column was charged with the above-modified active carbon in the same manner as described in Example 5 and a model emulsified oil was passed through it to test the oil fraction removal ability of the modified carbon, it was found that the treated water discharged had a turbidity of 15 ppm and this value was maintained even after ; ' ~ the passage of water for 25Q hours. The crude water starting material had a turbidity of 80 to 120 ppm.
15Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.
Claims (7)
1. An oil-containing waste water treating material, comprising:
an active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound having at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
an active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound having at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
2. The treating material of Claim 1, wherein said nitrogenous vinyl compound is dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxy-3-methacryloxy-propyltrimethylammonium chloride, methacrylic acid dimethyl-aminoethylmethyl chloride, 2-vinylpyridine or 4-vinylpyridine.
3. The treating material of Claim 1, which is a modified active carbon wherein at least one said nitrogenous vinyl compound is graft polymerized on the surface of said active carbon.
4. The treating material of Claim 1, which is a modified active carbon obtained by graft polymerizing a nitrogenous vinyl compound having an amine structure onto the surface of said active carbon and then treating said active carbon with a halide.
5. The treating material of Claim 1, which is a modified active carbon obtained by graft polymerizing a nitrogenous vinyl compound having an amine structure onto the surface of said active carbon, treating said active carbon subjected to graft polymerization with a halide, reacting a nitrogenous vinyl compound having an amine structure with the halide treated active carbon and then treating the product obtained with a halide.
6. The treating material of Claims 4 or 5 wherein said halide is hydrochloric acid, methyl iodide, methyl chloride or n-butyl bromide.
7. A method of removal of oil fractions from oil-containing waste water, comprising:
contacting said waste water with a bed of active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound having at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
contacting said waste water with a bed of active carbon upon whose surface is chemically bonded at least one nitrogenous vinyl compound having at least one structure selected from the group consisting of amine structures, and quaternary ammonium structures.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP102936/79 | 1979-08-13 | ||
| JP10293679A JPS5626972A (en) | 1979-08-13 | 1979-08-13 | Oil-containing waste water-treating material comprising modified active carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1143359A true CA1143359A (en) | 1983-03-22 |
Family
ID=14340719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000357402A Expired CA1143359A (en) | 1979-08-13 | 1980-07-31 | Oil-containing waste water treating material consisting of modified active carbon |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4320011A (en) |
| EP (1) | EP0025281B1 (en) |
| JP (1) | JPS5626972A (en) |
| CA (1) | CA1143359A (en) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58101737A (en) * | 1981-12-14 | 1983-06-17 | Mitsui Mining Co Ltd | Oil collecting carbonaceous material and its production |
| US4528281A (en) * | 1983-03-16 | 1985-07-09 | Calgon Carbon Corporation | Carbon molecular sieves and a process for their preparation and use |
| US4668403A (en) * | 1985-04-30 | 1987-05-26 | Betz Laboratories, Inc. | Process for reducing color contamination of influent water |
| US4765923A (en) * | 1985-04-30 | 1988-08-23 | Betz Laboratories, Inc. | Composition for reducing color contamination of influent water |
| US4668404A (en) * | 1985-04-30 | 1987-05-26 | Betz Laboratories, Inc. | Process for reducing color contamination of influent water |
| US4737293A (en) * | 1985-08-01 | 1988-04-12 | Betz Laboratories, Inc. | Process for reducing the content of trihalomethane compounds and precursors thereof in influent water |
| US4661259A (en) * | 1985-08-01 | 1987-04-28 | Betz Laboratories, Inc. | Process for reducing the content of trihalomethane compounds and precursors thereof in influent water |
| US4818293A (en) * | 1985-08-01 | 1989-04-04 | Betz Laboratories, Inc. | Stable slurries comprising powdered activated carbon |
| US4810266A (en) * | 1988-02-25 | 1989-03-07 | Allied-Signal Inc. | Carbon dioxide removal using aminated carbon molecular sieves |
| US5837790A (en) | 1994-10-24 | 1998-11-17 | Amcol International Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US5869550A (en) * | 1995-05-22 | 1999-02-09 | Cabot Corporation | Method to improve traction using silicon-treated carbon blacks |
| US5958999A (en) * | 1996-04-05 | 1999-09-28 | Cabot Corporation | Ink compositions and method for generating images produced therefrom |
| CN1113692C (en) * | 1996-06-14 | 2003-07-09 | 卡伯特公司 | Modified carbon adsorbents and process for adsorption |
| DE69706298T2 (en) * | 1996-06-14 | 2002-06-13 | Cabot Corp | MODIFIED COLORED PIGMENTS AND THIS INKERJET INK |
| US20020056686A1 (en) * | 1996-06-14 | 2002-05-16 | Agathagelos Kyrlidis | Chromatography and other adsorptions using modified carbon adsorbents |
| US5707432A (en) * | 1996-06-14 | 1998-01-13 | Cabot Corporation | Modified carbon products and inks and coatings containing modified carbon products |
| US6069190A (en) * | 1996-06-14 | 2000-05-30 | Cabot Corporation | Ink compositions having improved latency |
| US6110994A (en) * | 1996-06-14 | 2000-08-29 | Cabot Corporation | Polymeric products containing modified carbon products and methods of making and using the same |
| US6197274B1 (en) | 1996-09-25 | 2001-03-06 | Cabot Corporation | Silica coated carbon blacks |
| EP0929604A1 (en) * | 1996-09-25 | 1999-07-21 | Cabot Corporation | Pre-coupled silicon-treated carbon blacks |
| US6017980A (en) * | 1997-03-27 | 2000-01-25 | Cabot Corporation | Elastomeric compounds incorporating metal-treated carbon blacks |
| US5904762A (en) | 1997-04-18 | 1999-05-18 | Cabot Corporation | Method of making a multi-phase aggregate using a multi-stage process |
| US5895522A (en) * | 1997-08-12 | 1999-04-20 | Cabot Corporation | Modified carbon products with leaving groups and inks and coatings containing modified carbon products |
| US6068688A (en) * | 1997-11-12 | 2000-05-30 | Cabot Corporation | Particle having an attached stable free radical and methods of making the same |
| ATE312145T1 (en) | 1997-10-31 | 2005-12-15 | Cabot Corp | PARTICLES WITH A STABLE FREE RADICAL ATTACHED THERETO, POLYMERIZED MODIFIED PARTICLES AND METHOD FOR THE PRODUCTION THEREOF |
| US6368239B1 (en) | 1998-06-03 | 2002-04-09 | Cabot Corporation | Methods of making a particle having an attached stable free radical |
| US6387500B1 (en) | 1997-11-06 | 2002-05-14 | Cabot Corporation | Multi-layered coatings and coated paper and paperboards |
| US6472471B2 (en) | 1997-12-16 | 2002-10-29 | Cabot Corporation | Polymeric products containing modified carbon products and methods of making and using the same |
| US6103380A (en) * | 1998-06-03 | 2000-08-15 | Cabot Corporation | Particle having an attached halide group and methods of making the same |
| US6547854B1 (en) | 2001-09-25 | 2003-04-15 | The United States Of America As Represented By The United States Department Of Energy | Amine enriched solid sorbents for carbon dioxide capture |
| CN100410181C (en) * | 2006-10-22 | 2008-08-13 | 裴凤良 | Method for harnessing sewage using straw charcoal |
| CN105061758B (en) * | 2015-09-08 | 2017-04-12 | 大连碧水蓝天环保科技工程有限公司 | Preparation method of dendritic polyquaternium for treating oil-containing waste water |
| CN110368899A (en) * | 2019-07-16 | 2019-10-25 | 邱越 | A kind of absorbent charcoal composite material and its preparation method and application |
| CN114620984B (en) * | 2022-03-17 | 2022-11-29 | 江苏蓝羊羊装饰材料有限公司 | Decorative material and preparation method thereof |
| CN115845803A (en) * | 2022-12-22 | 2023-03-28 | 中新联科环境科技(安徽)有限公司 | Method for grafting and modifying activated carbon by quaternary ammonium salt |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3479299A (en) * | 1965-10-22 | 1969-11-18 | Cabot Corp | Carbon based catalysts and compositions producible therefrom |
| US3487928A (en) | 1966-10-06 | 1970-01-06 | Exxon Research Engineering Co | Process for the removal of dispersed droplets of oil from water |
| US3491031A (en) * | 1966-11-18 | 1970-01-20 | Calgon C0Rp | Reactivation of monoethanolamine impregnated activated carbon |
| US3755161A (en) * | 1970-02-05 | 1973-08-28 | Osaka Soda Co Ltd | Treatment process for removal of metals and treating agent therefor |
| US3813347A (en) * | 1970-10-05 | 1974-05-28 | Universal Oil Prod Co | Manufacture of adsorbent composite |
| JPS4817438B1 (en) * | 1970-12-29 | 1973-05-29 | ||
| FR2127432A5 (en) | 1971-03-01 | 1972-10-13 | Monsan Pierre | |
| US3901818A (en) * | 1971-03-01 | 1975-08-26 | Creusot Loire | Hydrocarbon binding complex and process for its preparation |
| JPS5522409B2 (en) * | 1971-08-20 | 1980-06-17 | ||
| FR2223063B2 (en) | 1973-03-28 | 1976-09-10 | Creusot Loire | |
| JPS5210675B2 (en) * | 1973-07-14 | 1977-03-25 | ||
| CA1060728A (en) * | 1973-07-26 | 1979-08-21 | Jack Fennimore | Treatment of particulate carbon with biocompatible polymer |
| JPS5324190B2 (en) * | 1974-03-05 | 1978-07-19 | ||
| JPS51136591A (en) * | 1975-05-22 | 1976-11-26 | Gosei Kagaku Kenkyusho:Kk | Method for separating oil and water |
| FR2313325A1 (en) | 1975-06-05 | 1976-12-31 | Creusot Loire | PROCESS AND EQUIPMENT FOR TREATING AN EFFLUENT POLLUTED BY COLLOIDAL EMULSIONS |
| JPS5248581A (en) * | 1975-10-15 | 1977-04-18 | Jgc Corp | Oil collecting agent |
-
1979
- 1979-08-13 JP JP10293679A patent/JPS5626972A/en active Pending
-
1980
- 1980-07-31 CA CA000357402A patent/CA1143359A/en not_active Expired
- 1980-08-07 US US06/176,052 patent/US4320011A/en not_active Expired - Lifetime
- 1980-08-13 EP EP80302797A patent/EP0025281B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0025281A1 (en) | 1981-03-18 |
| JPS5626972A (en) | 1981-03-16 |
| EP0025281B1 (en) | 1983-04-06 |
| US4320011A (en) | 1982-03-16 |
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