IE902283A1 - Process and apparatus for the treatment of effluents containing emulsion inks - Google Patents
Process and apparatus for the treatment of effluents containing emulsion inksInfo
- Publication number
- IE902283A1 IE902283A1 IE228390A IE228390A IE902283A1 IE 902283 A1 IE902283 A1 IE 902283A1 IE 228390 A IE228390 A IE 228390A IE 228390 A IE228390 A IE 228390A IE 902283 A1 IE902283 A1 IE 902283A1
- Authority
- IE
- Ireland
- Prior art keywords
- effluent
- inks
- process according
- sludge
- centrifuging
- Prior art date
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
- C02F1/385—Treatment of water, waste water, or sewage by centrifugal separation by centrifuging suspensions
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
- Colloid Chemistry (AREA)
- Centrifugal Separators (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Method and device for the treatment of effluents containing inks, especially water-based inks, by separation, with a view to obtaining, on the one hand, sludge containing the inks and, on the other hand, the clarified effluent. According to the invention a flocculation of the effluent is carried out by the action of a flocculating agent followed by continuous centrifuging of the effluent, consisting of an acceleration of between 1,000 and 20,000 g while avoiding an air-liquid interface during the centrifuging. Application of the invention to the treatment of effluents containing water-based inks, from paper mills, cardboard manufacturing plants and bag manufacturing plants. <IMAGE>
Description
PROCESS AND APPARATUS FOR THE TREATMENT OF EFFLUENTS CONTAINING EMULSION INKS The invention relates to the treatment of effluents containing inks, particularly emulsion inks, used in printing processes in printing works and in all other industries such as e.g. paper, cardboard and similar factories.
In the industries involved in the transformation of paper or cardboard, the effluents to be treated can contain various pollutants and in particular emulsion inks, particularly when the industrial installation uses a flexographic printing process. They may also contain adhesive residues, e.g. based on starch.
In order to treat these effluents, numerous processes have already been proposed. They generally consist of separating by different methods the polluting agents from the water containing them, in order to obtain on one side polluting sludge and on the other the clarified effluent.
The polluting sludge obtained is then eliminated, generally by incineration.
Thus, a flocculation-based separating process has been proposed, which is followed the static decanting of the effluents. However, the sludge obtained through the performance of this process is not very dense, so that the volume to be destroyed is considerable and incineration costs are high.
In order to obtain more compact sludge, it is already been proposed to use a filter press making it possible to pass from a dryness of 2 to 3% to a dryness of approximately 30%. However, one of the disadvantages of the filter press is that its flow rate is variable being linked with the clogging of the cloths, which can occur rapidly. - 2 The filter press also requires man power for monitoring it, particularly at the time of removing the cake.
In addition, a ultra-filtration separating process has been proposed. However, this is an onerous process and the problem of membrane or cloth clogging again occurs. .
This can also be irreversible in the case of products such as hydrocarbons, oils and special adhesives.
The invention proposes a process for the treatment of effluents making it possible to in particular separate the inks from the water containing them and obtain on the one side a clarified effluent and simultaneously on the other side particularly compact sludge.
According to the invention, the effluent is treated with the aid of a flocculating agent and the effluent then undergoes continuous centrifuging involving an acceleration between 1000 and 20,000 g and preferably 1000 and 11,000 g, whilst avoiding an air-liquid interface during centrifuging.
Within the terms of the invention, continuous centrifuging means centrifuging in which the supply of effluent on the one hand and the discharge of the darified effluent of the other are continuous, at least between two washing operations .
By avoiding any air-liqiud interface during centrifuging, any risk of foam forming due to the presence of air on the surface of the effluent is obviated. The formation of a foam can greatly reduce the efficiency of separation of inks from water.
According to one of the aspects of the invention, flocculation takes place in an acid medium and in particular at a pH between 2 and 6, by using a flocculating agent chosen - 3 from among mineral flocculents, such as aluminium sulphate, aluminium sulphate polymers, ferric chloride, as well as organic flocculants such as ionic or non-ionic polymers.
Preferably, flocculation takes place at a pH of approximately 5 by adding an acid, such as sulphuric acid and the flocculating agent is constituted by at least one agent chosen from among the cationic polymers, such as modified or unmodified polyethylene-imines and aluminium sulphates.
In order to still further improve the flocculation efficiency this can advantageously be carried out in certain cases with an adequate stirring.
The flocculating agent quantity can vary as a function of the type of agent and the type of effluent to be treated. Generally a flocculating agent level of 0.1 to 2% by weight based on the weight of dry matter in the effluent is chosen. The flocculation stage can be very short lasting only a few seconds.
In order to improve the following centrifuging, to the effluent is advantageously added, particularly during flocculation, an antifoaming agent. A suitable antifoaming agent is e.g. silicone oil.
According to an advantageous feature of the invention, to the effluent is also added a starch-based adhesive, when the effluent does not contain such an adhesive or only contains a very small amount of it. Tests according to the invention have revealed that the presence of a starch adhesive in the effluent further increases the dryness of the sludge obtained by centrifuging. For example, an effluent containing approximately lg/1 of a starch-based adhesive prior to centrifuging, can be reduced after centrifuging to a sludge volume of approximately 5 to 6% of the total volume of the effluent, the remainder - 4 being clarified effluent, whereas an effluent of the same type, but without starch, can only be reduced after centrifuging to a sludge volume of approximately 10%.
It would appear that the starch brings about a compacting of the inks, which appear in flake form after flocculation.
This phenomenon is linked with the inventive process, which utilises a continuous effluent supply to the centrifuge.
The quantity of starch-based adhesive advantageously added to the effluent corresponds to the obtaining of a starch adhesive level, expressed in dry matter in the effluent, between approximately 0.1 and 10 kg/m·^ of effluent and preferably between 0.1 and 2 kg/m^.
The invention also relates to an apparatus or installation for the treatment of effluents containing emulsion inks.
The apparatus comprises in combination means for mixing the flocculating agent and, if appropriate the other additives, with the effluent, as well as a disk-type industrial centrifuge, positioned downstream of said mixing means and which operates on a full bowl principle, in order to separate the sludge containing the inks from the clarified effluent.
A full bowl operation means, according to the invention, that during centrifuging the bowl is full with effluents to be separated and therefore has no air-liquid interface.
In such a centrifuge the clarified effluent is continuously separated .
The sludge containing the inks is ejected from the rotating bowl, either continuously through nozzles, or at periodical intervals by opening the bowl.
According to a feature of the apparatus, the mixing means comprise a reaction tank or vessel in which flocculation takes place. If appropriate, the reaction tank can be equipped with a stirrer. - 5 According to a variant, the means for mixing the flocculating agent and, if appropriate the other additives, with the effluent are the supply pipes for the centrifuge, the introduction of the flocculating agent and the other additive taking place directly in said pipe, which then acts as a static mixer.
In another variant, the mixing of the effluent with the flocculating agent and the flocculation can take place both in the supply pipe and in a reaction tank upstream of the centrifuge.
Fig.l diagrammatically shows an embodiment of a treatment installation according to the invention. In said Fig.l, a vessel 1 makes it possible to store the effluents to be treated 2, e.g. flexographic liquors. A pipe 3 incorporating a supply pump 4 is located between the storage vessel 1 and a reaction tank 5, in which the flocculation takes place following the injection or addition of a flocculating agent 6 in pipe 3 upstream of the reaction tank.
Injections or additions of other products or additives can take place in the reaction tank or advantageously in the supply pipe 3 upstream of said tank. In particular, it is possible to inject an acid in order to raise the effluent to the desired pH. It is also possible to add an antifoaming agent and/or a starch-based adhesive.
On leaving the reaction tank 5, the effluent containing the flakes is supplied by the pipe 8 to the centrifugal clarifier or centrifuge 9, which separates the sludge containing the inks discharged by pipe 11 into the sludge tank 12 from the clarified effluents 13 discharged by pipe 14.
The installation according to the embodiment also comprises a pipe 15 permitting the return of the effluents from - 6 the centrifuge to the storage tank 1, in the case of an operating incident in the installation, e.g. a bad separation of the sludges, and if the effluent is not clarified enough.
Another pipe 16 can be provided between the sludge tank and the storage tank, said pipe 16 emanating from the sludge tank at the desired level. Thus, it is necessary to provide for periodic opening of the centrifuge bowl in order to discharge the sludge. This obviously applies for a centrifuge operating by opening circular orifices at periodic intervals for discharging the sludge, but also for a nozzle-equipped centrifuge which, although discharging the sludge on a continuous basis, still requires its bowl to be opened periodically. Whenever the centrifuge bowl is opened, the liquid contained in the bowl is discharged at the same time as the sludge in the sludge tank and finally it is possible for the sludge tank to contain at an intermediate level between the upper level containing the aerated flakes and the lower level containing the decanted matter, a phase less charged with dry matter, which can then be advantageously recycled and reprocessed.
A not shown, auxiliary cleaning circuit can complete the installation .
Fig.2 diagrammatically shows a disk-type centrifuge 9, which can be used in the installation shown in Fig.l.
A suitable centrifuge is e.g. a periodic ejection separator, also known as an auto-cleaning bowl separator. In such a separator 9 with disks 17, the rotary bowl 18 is biconical. In the junction plane of the cones are located either nozzles, or circular orifices, which can be open or closed. When the circular orifices are closed, the sludge or solids 10 accumulate in the space between the bowl 18 and the disks 17. When they are open, the solids are discharged to the outside. This type of separator is e.g. marketed by WESTFALIA SEPARATOR. The supply of effluents 8 containing flakes is continuous and takes place at the centre of the - 7 bowl by pipe 19. The sludge 10 gradually accumulates in the vicinity of the circular orifice 20 and the clarified effluent 13 is discharged by the discharge pipe 14. On opening the bowl by the action of the piston 21, the sludge 10 is ejected and discharged by pipe 11. The bowl rotating at high speed is driven by the shaft 22. The bowl can be opened and closed manually, or can be brought about at regular intervals, or can be controlled by the separator when the sludge reaches a certain volume.
The invention is applicable to the treatment of different effluents and in particular those of the following types: wash water containing inks for flexographic printing and wash water for flexographic printing containing starchbased adhesive.
When the effluent to be treated contains other pollutants, particularly those which are immiscible with water such as oils, prior to carrying out the process according to the invention, it can be advantageous to carry out other separation treatments on the effluent, e.g. a separation of the oil by florentine.
Other feature and advantages of the invention can be gathered from the following examples.
EXAMPLE 1 An effluent containing flexographic printing inks is treated by using the installation shown in Fig.l. Prior to treatment, said effluent has a dry matter content of 27 g/1.
Sulphuric acid is injected into pipe 3 in order to acidify the effluent to pH 5. This is followed by the injection of a flocculating agent, namely polyethylene-imine, at a rate of 1.3kg of a commercial solution with 25% dry matter per m3. To pipe 3 is also added a silicone oil as an antifoaming agent, at a rate of 125g of commercial - 8 solution per m3. Following a passage in the reaction tank 5, which lasts approximately 10 to 20 seconds, the effluent is passed into the continuously operating centrifuge, e.g. that marketed by WESTFALIA SEPARATOR under the name clarifier SA 20.
In said clarifier the effluent undergoes a maximum acceleration of 7,000g and the effluent flow rate is 0.75m3/h. On leaving the clarifier, on one side is obtained the clarified effluent discharged by pipe 14 and on the other side is sludge containing the inks, discharged by the pipe 11 in to the sludge tank 12. The sludge in the sludge tank represents 90g/l and their volume corresponds to approximately 25% of the initial effluent volume. The sludge can be incinerated .
EXAMPLE 2 An effluent containing water-soluble inks for flexographic printing is treated. Prior to treatment, said effluent has a dry matter content of 8.7g/l. The procedure of Example 1 is followed for all the prior treatments, whilst adjusting the quantities to the dry matter content of the effluent. The effluent undergoes centrifuging, the effluent flow rate in the centrifuge being regulated to 2m3/h.
Sludge is obtained with a dry matter content of approximately 90g/l. The sludge volume corresponds to approximately 9% of the initial effluent volume.
EXAMPLE 3 The effluent of Example 2 is treated by also adding to pipe 3, upstream of the reaction tank 5, a starch-based adhesive at a rate of 1kg of dry matter per m3 of effluent.
The effluent then undergoes centrifuging as in Example 2. - 9 Sludge is obtained with a dry matter content of approximately 220 g/1, whose volume corresponds to 4% of the initial effluent volume. Compared with Example 2, it should be noted that the addition of starch greatly improves the sludge compacting process by centrifuging.
Claims (18)
1. Process for the treatment of effluents containing inks and in particular emulsion inks, by separation, with a view to obtaining on one side sludge containing the inks and on the other side the clarified effluent, characterized in that the effluent is flocculated by the action of a flocculating agent, followed by a continuous centrifuging of the effluent consisting of an acceleration between 1,000 and 20,000 g, whilst avoiding an air-liquid interface during centrifuging.
2. Process according to claim 1, characterized in that the flocculation is carried out in an acid medium.
3. Process according to claim 2, characterized in that the flocculation is carried out by raising the effluent to a pH of approximately 5 by adding an acid and in that the flocculating agent is constituted by a cationic polymer chosen from among modified or unmodified polyethyleneimines .
4. Process according to one of the claims 1 to 3, characterized in that flocculation is accompanied by stirring.
5. Process according to one of the claims 1 to 4, characterized in that an antifoaming agent is added to the effluent prior to centrifuging.
6. Process according to one of the claims 1 to 5, characterized in that a starch-based adhesive is added to the effluent prior to centrifuging, when the latter contains little or no such adhesive.
7. Process according to claim 6, characterized in that the starch-based adhesive is added in order to obtain a starch-based adhesive level, expressed as dry matter - 11 in the effluent, between 0.1 and 10 kg/m^ of effluent and preferably between 0.1 and 2 kg/m^ of effluent.
8. Process according to one of the claims 1 to 7, characterized in that the centrifuging consist s of an acceleration at between 1,000 and 11,000 g.
9. Apparatus for performing the process according to one of the claims 1 to 8, characterized in that it comprises means for mixing the flocculating agent with the effluent, said means being located just upstream of an industrial disk-type centrifuge operating continuously on the full bowl principle separating on the one side the sludge containing the inks and on the other side the clarified effluent.
10. Apparatus according to claim 9, characterized in that the disk centrifuge is a self-cleaning bowl separator with periodic opening or continuous discharge of the sludge.
11. Apparatus according to one of the claims 9 or 10, characterized in that the means for mixing the flocculating agent with the effluent comprise a flocculating tank or vessel.
12. Apparatus according to one of the claims 9 or 10, characterized in that the means for mixing the flocculating agent with the effluent are esentially formed by the pipe for supplying effluent to the disk centrifuge, the flocculating agent being directly introduced into said pipe, which acts as a static mixer.
13. Apparatus according to one of the claims 9 to 12, characterized in that it comprises a recycling circuit for the sludge phases not containing dry matter and taken up downstream of the centrifuge. - 12
14. Apparatus according to one of the claims 9 to 13, characterized in that it comprises a recycling circuit which could be used in the case of an operating incident and if the effluent is not clarified enough.
15. Application of the process according to one of the claims 1 to 8, to the treatment of containing emulsion inks from paper, cardboard and similar factories.
16. Process for the treatment of effluents containing inks and in particular emulsion inks substantially as herein described with reference to the accompanying drawings.
17. Apparatus for the treatment of effluents containing inks and in particular emulsion inks substantially as herein described with reference to and as shown in the accompanying drawings.
18. The features described in the foregoing specification, or any obvious equivalent thereof, in any novel selection.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8908673A FR2649091B1 (en) | 1989-06-29 | 1989-06-29 | PROCESS AND DEVICE FOR THE TREATMENT OF EFFLUENTS CONTAINING INKS WITH WATER |
Publications (3)
Publication Number | Publication Date |
---|---|
IE902283L IE902283L (en) | 1990-12-29 |
IE902283A1 true IE902283A1 (en) | 1991-01-16 |
IE62409B1 IE62409B1 (en) | 1995-01-25 |
Family
ID=9383249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE228390A IE62409B1 (en) | 1989-06-29 | 1990-06-25 | Process and apparatus for the treatment of effluents containing emulsion inks |
Country Status (17)
Country | Link |
---|---|
EP (1) | EP0406105B1 (en) |
JP (1) | JPH03131384A (en) |
KR (1) | KR910000543A (en) |
AT (1) | ATE104253T1 (en) |
BR (1) | BR9003069A (en) |
CA (1) | CA2020069A1 (en) |
DD (1) | DD296262A5 (en) |
DE (1) | DE69008054T2 (en) |
DK (1) | DK0406105T3 (en) |
ES (1) | ES2055362T3 (en) |
FI (1) | FI903273A0 (en) |
FR (1) | FR2649091B1 (en) |
IE (1) | IE62409B1 (en) |
NO (1) | NO902889L (en) |
PT (1) | PT94518A (en) |
TR (1) | TR27358A (en) |
ZA (1) | ZA904812B (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1251800B (en) * | 1991-07-15 | 1995-05-26 | Comer Spa | PROCEDURE AND PLANT FOR CLARIFYING WASHING WATERS |
GB9116701D0 (en) * | 1991-08-02 | 1991-09-18 | Allied Colloids Ltd | Dewatering of aqueous suspensions |
GB9116702D0 (en) * | 1991-08-02 | 1991-09-18 | Allied Colloids Ltd | Dewatering of aqueous suspensions |
US5681480A (en) * | 1991-08-02 | 1997-10-28 | Allied Colloids Limited | Dewatering of aqueous suspensions |
US5320873A (en) * | 1991-08-29 | 1994-06-14 | American Laundry Machinery, Inc. | Process and apparatus for treating cellulosic fiber-containing fabric to improve durable press and shrinkage resistance |
DE4138667A1 (en) * | 1991-11-25 | 1993-05-27 | Sued Chemie Ag | METHOD FOR DISCHARGING DRAIN CLEANER |
EP2363290A1 (en) * | 2010-03-05 | 2011-09-07 | KBA-NotaSys SA | Installation and process for recycling wiping solution of one or more intaglio printing presses |
CN102757159B (en) * | 2012-08-08 | 2014-08-20 | 南京大学 | Novel papermaking black liquor treatment method and system |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1101301B (en) * | 1957-08-23 | 1961-03-02 | Krauss Maffei Ag | Method and device for thickening sludge, in particular sewage sludge, which contains constituents that are difficult to sediment, by centrifugation using a flocculant |
US4076578A (en) * | 1974-10-21 | 1978-02-28 | Canadian Patents And Development Limited | Ink removal from waste paper |
JPS5959257A (en) * | 1982-09-27 | 1984-04-05 | Mitsubishi Heavy Ind Ltd | Deinking system |
-
1989
- 1989-06-29 FR FR8908673A patent/FR2649091B1/en not_active Expired - Fee Related
-
1990
- 1990-06-21 ZA ZA904812A patent/ZA904812B/en unknown
- 1990-06-25 IE IE228390A patent/IE62409B1/en not_active IP Right Cessation
- 1990-06-27 PT PT94518A patent/PT94518A/en not_active Application Discontinuation
- 1990-06-27 DE DE69008054T patent/DE69008054T2/en not_active Expired - Fee Related
- 1990-06-27 ES ES90401837T patent/ES2055362T3/en not_active Expired - Lifetime
- 1990-06-27 DK DK90401837T patent/DK0406105T3/en active
- 1990-06-27 KR KR1019900009534A patent/KR910000543A/en not_active Application Discontinuation
- 1990-06-27 AT AT90401837T patent/ATE104253T1/en not_active IP Right Cessation
- 1990-06-27 EP EP19900401837 patent/EP0406105B1/en not_active Expired - Lifetime
- 1990-06-28 NO NO90902889A patent/NO902889L/en unknown
- 1990-06-28 FI FI903273A patent/FI903273A0/en not_active IP Right Cessation
- 1990-06-28 JP JP2168609A patent/JPH03131384A/en active Pending
- 1990-06-28 CA CA 2020069 patent/CA2020069A1/en not_active Abandoned
- 1990-06-29 DD DD90342283A patent/DD296262A5/en not_active IP Right Cessation
- 1990-06-29 BR BR9003069A patent/BR9003069A/en not_active Application Discontinuation
- 1990-07-30 TR TR68690A patent/TR27358A/en unknown
Also Published As
Publication number | Publication date |
---|---|
PT94518A (en) | 1991-02-08 |
DE69008054T2 (en) | 1994-10-27 |
NO902889L (en) | 1991-01-02 |
CA2020069A1 (en) | 1990-12-30 |
NO902889D0 (en) | 1990-06-28 |
FI903273A0 (en) | 1990-06-28 |
EP0406105A1 (en) | 1991-01-02 |
IE62409B1 (en) | 1995-01-25 |
FR2649091A1 (en) | 1991-01-04 |
KR910000543A (en) | 1991-01-29 |
JPH03131384A (en) | 1991-06-04 |
IE902283L (en) | 1990-12-29 |
EP0406105B1 (en) | 1994-04-13 |
BR9003069A (en) | 1991-08-27 |
DD296262A5 (en) | 1991-11-28 |
ZA904812B (en) | 1991-04-24 |
TR27358A (en) | 1995-01-17 |
DK0406105T3 (en) | 1994-08-29 |
ATE104253T1 (en) | 1994-04-15 |
DE69008054D1 (en) | 1994-05-19 |
FR2649091B1 (en) | 1991-10-04 |
ES2055362T3 (en) | 1994-08-16 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Patent lapsed |