Patent Application
20200102239
The present invention relates to a method of treating sludge in order to improve dewatering of the sludge.
Sludge may be obtained from different applications. Wastewater treatment plants may receive municipal and/or industrial wastewaters. During the wastewater treatments sludges are obtained. Depending on the amount of treatments performed and type of incoming wastewater the obtained sludges may be more or less difficult to process further. The sludge obtained may not always be an asset so ways to decrease the amount of sludge is attractive. Sludge may need to be incinerated or put on landfill sites. However, this may be costly in view of large volumes to handle, e.g. in view of transport costs, large areas needed for deposits or low incineration efficiency.
Sludge dewatering is the separation of a liquid and solid phase whereby, generally, the least possible residual moisture is required in the solid phase for the reason that the residual moisture in the dewatered solids determines the disposal costs. Current main sludge dewatering solutions are mainly based on chemical conditioning of sludge followed by physical based equipment treatment.
In some applications and/or countries dewatering of sludge is improved by addition of mineral additives (skeleton builders), such as lime, gypsum, ash, red mud or cement at very high dosages. Such additives are added as mineral filtration aids. The upside of addition of such compounds is that it increases the dry solids (DS) content of the final sludge dramatically, especially with lime, as lime reacts in contact with water and increases in volume. However, the downside is that the total amount of dewatered sludge cake to handle further has increased drastically, resulting in high handling costs of the voluminous sludge cake. Thus, an improved dewatering does not always provide a good overall economical solution.
Thus, there is a need to further improve the dewatering of sludges and avoid or decrease the use of skeleton builders. An important advantage for dewatering processes lies in reduced sludge disposal costs associated with producing a drier dewatered sludge cake.
The present invention relates to a method of treating municipal and/or industrial sludge comprising the steps of:
In one embodiment the catalyst may be selected from metals salts of the group consisting of salts of iron, copper, manganese, titanium, cobalt, aluminium, and cerium, and any combination thereof, preferably selected from the group consisting of salts of copper(II), ferrous and ferric iron.
In one embodiment the metals salts may be selected from the group chlorides, sulfates and oxides, and any combination thereof.
In one embodiment the metals salts may be selected from the group consisting of iron sulfate, iron chloride, iron oxide, copper chloride, copper sulfate, cobalt chloride, manganese oxide, titanium oxide, aluminium oxide, cerium oxide, and any combination thereof.
In one embodiment the catalyst may be provided to the sludge in an amount of 10-120 kg per tonne of sludge dry solids (kg/tDS), preferably 20-80 kg/tDS, preferably 30-50 kg/tDS.
In one embodiment the radical initiator may be selected from the group hydrogen peroxide, sodium percarbonate and sodium perborate, and sodium persulfate, and any combination thereof, preferably selected from the group hydrogen peroxide, and sodium persulfate, and any combination thereof.
In one embodiment when the radical initiator is hydrogen peroxide, step b) may be performed before step c).
In one embodiment when the radical initiator is sodium persulfate, step c) may be performed before step b).
In one embodiment the radical initiator may be added to the sludge in an amount of at most 200 kg per tonne of sludge dry solids (kg/tDS), preferably 5-150 kg/tDS.
In one embodiment the polymer may be an anionic, cationic or nonionic polymer. It may be selected from the group polyacrylamide, polyamine, polyDADMAC, melamine formaldehydes, natural polymers, such as tannins and lignin, natural polysaccharides, such as starch, cellulose, hemicellulose alginate, guar gum, pectin, chitin and chitosan, and cationic or anionic derivatives thereof, and any combination thereof. For example, the compounds may be selected from polyacrylamide, polyamine and polyDADMAC, and any combination thereof.
In one embodiment polyacrylamide may have a standard viscosity of at least 2 mPa·s measured at 0.1 weight-% solids content in an aqueous NaCl solution (1 M), at 25° C., using Brookfield DVII T viscometer with UL adapter.
In one embodiment the polymer may be added to the sludge in an amount of 0.5-10 kg per tonne of sludge dry solids (kg/tDS), such as 0.75-6 kg/tDS, 1-4 kg/tDS, or 1-3 kg/tDS.
In one embodiment the method may further comprise providing a defoamer to the sludge before step d) and after steps b) and c), preferably selected from the groups silicone fluid (polysiloxane) defoamers or modified silicone fluid defoamers or silicone compound defoamers.
In one embodiment step e) may be performed by a separation selected from sedimentation, flotation, pressing, centrifugation and filtration, and any combination thereof, preferably by using a device selected from the group consisting of decanter centrifuge, rotary screen, belt press, filter press, disc filter press, screw press.
In one embodiment the dewatered sludge cake may have dry solids content (DS) of at least 30 wt %, such as at least 40 wt % DS.
In one embodiment the sludge to be treated may be from wastewater purification.
In one embodiment the sludge to be treated may be selected from undigested sludge, digested sludge, chemically treated sludge, and dewatered sludge, and any combination thereof. This incoming sludge has a pH of at least 6.
In one embodiment the sludge of step a) has a pH of 6-8.5, such as pH 6-8, or pH 6.5-8.
The present invention relates to a method of treating municipal and/or industrial sludge comprising the steps of:
a) providing the sludge, which has a pH of at least 6;
b) adding a catalyst to said sludge;
c) adding a radical initiator, selected from hydrogen peroxide and percompounds, to said sludge;
d) adding a polymer to said sludge to provide a chemically treated sludge;
e) dewatering said chemically treated sludge in at least one stage to provide a dewatered sludge cake;
wherein step b) and c) may be performed in any order.
The present method is used to condition incoming sludge in stages before dewatering. The chemicals used are added in a sequence. However, the addition of the radical initiator and catalyst may change places in the above mentioned order.
The catalyst may be selected from metals salts of the group consisting of salts of iron, copper, cobalt, manganese, titanium, aluminium, and cerium, and any combination thereof. Examples of catalysts which are usable may be selected from the group consisting of salts of copper(II), ferrous and ferric iron.
The present metals salts may be selected from different types, e.g. the group consisting of chlorides, sulfates and oxides, and any combination thereof.
Examples of suitable metal salts may be selected from the group consisting of iron sulfate, iron chloride, iron oxide, copper chloride, copper sulfate, cobalt chloride, manganese oxide, titanium oxide, aluminium oxide, cerium oxide, and any combination thereof. Metal salts that may be preferred to use in the present process may be selected from FeSO4, Fe2(SO4)3, FeCl3, CuCl2, CoCl2, CuSO4, MnO2, TiO2, Al2O3, Fe2O3, and CeO2.
The amount of catalyst added may naturally vary, but the catalyst may be provided to the sludge in an amount of 10-120 kg per tonne of sludge dry solids (kg/tDS), such as 20-80 kg/tDS, or 30-50 kg/tDS.
The catalyst may be mixed with the sludge of a time period of about 0.5-30 min, such as about 1-15 min, about 2-5 min, or about 5-10 min.
Also, it is to be noted that some catalysts may also function as coagulants. However, not all catalysts may have that ability.
The present process also includes addition of a radical initiator. An important role of radical initiators suitable for the present method is that they are able to form into radicals. They are a source of radicals. The formation of radicals is an important step for the present method. The radical initiator may also be capable of oxidizing material, i.e. it may act as an oxidant.
Certain metal ions, as present catalysts, cause decomposition with formation of free radicals, such as (HO.) and (HOO.) being formed. Hydroxyl radicals (.OH) are e.g. formed from the reaction (I):
Fe2++H2O2→Fe3++.OH+OH− (I).
Superoxide radicals (HOO.) are e.g. formed from the reaction (II):
Fe3++H2O2→Fe2++HOO.+H+ (II).
The radicals have very high redox potential, which is then utilized to rupture the cell and release the intracellular water.
Percompounds, such as those including sulfates, may be used as radical initiators.
Sulfate radicals (SO4−.) are e.g. formed through the reaction (III):
S2O82−+Mn+→M(n+1)++SO4−.+SO42− (III).
The sulfate radicals (SO4−.) have an even higher redox potential estimated to be 2.60V, similar to that of hydroxyl radical (.OH, 2.70V), which is then utilized to rupture the cell and release the intracellular water.
The radical initiator may be selected from the group consisting of hydrogen peroxide, sodium percarbonate, sodium perborate, and sodium persulfate, and any combination thereof. The radical initiator may preferably be selected from the group consisting of hydrogen peroxide, and sodium persulfate, and any combination thereof.
The present process may provide the radical initiator in different orders. A choice of order may be influenced by the type of radical initiator used. For example, when the radical initiator is hydrogen peroxide, step b) may be performed before step c). In another example, when the radical initiator is a percompound, e.g. sodium persulfate, step c) may be performed before step b).
When the radical initiator is added before the catalyst, the radical initiator may be provided as a solid. If the radical initiator is a percompound it may be provided to the sludge as solids. Thus, e.g. sodium persulfate may be provided in solid form to the sludge being treated.
When hydrogen peroxide is used as radical initiator, no acidification is performed on the incoming sludge before addition of radical initiator and catalyst. Then it is preferred to use FeCl3 and/or CuCl2 as catalyst, which preferably is added before the hydrogen peroxide to the sludge.
When sodium persulfate is used as radical initiator, no acidification is performed on the incoming sludge before addition of radical initiator and catalyst. Then it is preferred to use a metal salt selected from Fe2+, Fe3+, and Cu2+ as catalyst, which is added after the sodium persulfate to the sludge, preferably the metal salt is CuCl2. During tests of the present method it was found that when sodium persulfate was used, preferably a combination with Cu2+ as catalyst provided the best results in view of producing the driest sludge cake after dewatering.
The radical initiator may be added to the sludge in an amount of at most 200 kg per tonne of sludge dry solids (kg/tDS), such as about 5-150 kg/tDS.
As an example, when the radical initiator is hydrogen peroxide, it may be added to the sludge in an amount of 5-80 kg per tonne of sludge dry solids (kg/tDS), such as 10-60 kg/tDS, or 20-35 kg/tDS. It is preferable to keep the hydrogen peroxide amount within the present ranges as overdosing may provide a risk of foam forming which is undesirable.
As an example, when the radical initiator is a percompound, e.g. sodium persulfate, it may be added to the sludge in an amount of 20-150 kg per tonne of sludge dry solids (kg/tDS), such as 30-120 kg/tDS, or 50-150 kg/tDS.
The radical initiator may be mixed with the sludge of a time period of about 0.5-30 min, such as about 1-15 min, about 2-5 min, or about 5-10 min.
As mentioned above, the different steps b) and c) may be switched in order. Whichever comes first of step b) and c) may be mixed with the sludge of a time period of about 2-5 min, and the latter step then being mixed for about 5-10 min.
The polymer that is provided in step d) may be an anionic, a cationic or a nonionic polymer. Many different types of polymers may be used in the present process, and such may be selected from the group polyacrylamide, polyamine, polyDADMAC, melamine formaldehydes, natural polymers, such as tannins and lignin, natural polysaccharides, such as starch, cellulose, hemicellulose alginate, guar gum, pectin, chitin and chitosan, and cationic or anionic derivatives thereof, and any combination thereof. For example, the compounds may be selected from polyacrylamide, polyamine and polyDADMAC, and any combination thereof.
The polymer may have a high molecular weight. The molecular weight may be defined in terms of the standard viscosity (SV), e.g. herein measured at 0.1 weight-% solids content in an aqueous NaCI solution (1 M), at 25° C., using Brookfield DVII T viscometer with UL adapter. If the polymer is polyacrylamide, it may have a SV of at least 2 mPa·s, such as above 2 mPa·s, about 2-9 mPa·s, about 2.2-8 mPa·s, or about 2.5-7 mPa·s, measured at 0.1 weight-% solids content in an aqueous NaCI solution (1 M), at 25° C., using Brookfield DVII T viscometer with UL adapter. In preferred embodiments the polymer may be selected from linear or structured dry poly-acrylamides with a standard viscosity of >2 mPa·s, measured at 0.1 weight-% solids content in an aqueous NaCl solution (1 M), at 25° C., using Brookfield DVII T viscometer with UL adapter; linear or structured emulsion poly-acrylamides with a standard viscosity of >2 mPa·s, measured at 0.1 weight-% solids content in an aqueous NaCl solution (1 M), at 25° C., using Brookfield DVII T viscometer with UL adapter; polydiallyldimethylammonium chlorides (poly-DADMACs); and poly-amines. The polyamines may have a molecular weight of about 10 000 to about 500 000 Da, preferably about 10 000 to about 300 000 Da. The polyDADMACs may have a molecular weight of about 100 000 to about 500 000 Da, preferably about 100 000 to about 300 000 Da. The polyamines or polyDADMACs may be selected from anionic, nonionic and cationic polymers, and any combination thereof. Preferably the polymer is selected from the group cationic polyamine and cationic polydiallyldimethylammonium chloride (polyDADMAC), and any combination.
The polymer may be added to the sludge in an amount of 0.5-10 kg per tonne of sludge dry solids (kg/tDS), such as about 0.75-6 kg/tDS, about 1-4 kg/tDS, or about 1-3 kg/tDS. These amounts are in view of total solids of the polymer used.
The polymer may be mixed with the sludge of a time period of about 1 second to 10 min, such as about 1-5 seconds, about 0.2-1 min, or about 5-10 min.
If the incoming sludge of the process is municipal sludge the use of cationic polymers may be preferred. If the incoming sludge is industrial sludge the use of anionic polymers may be preferred.
The present method may further comprise providing a defoamer to the sludge before step d) and after steps b) and c). The defoamer may be selected from the groups silicone fluid (polysiloxane) defoamers or modified silicone fluid defoamers, or silicone compound.
Step e) may be performed by a separation selected from sedimentation, flotation, pressing, centrifugation and filtration, and any combination thereof, preferably by using a device selected from the group consisting of decanter centrifuge, rotary screen, belt press, filter press, disc filter press, screw press.
The dewatered sludge cake obtained in step e) may have dry solids content (DS) of at least 30 wt %, such as at least 40 wt % DS.
The incoming sludge of the present process may be obtained from wastewater treatment. The incoming sludge may be obtained from one wastewater treatment step or a mixture of several wastewater treatment steps. The incoming sludge to be treated with the present process may be selected from undigested sludge, digested sludge, chemically treated sludge, and dewatered sludge, and any combination thereof. Combinations of the above mentioned sludges may be used, so if the sludge to be treated is dewatered sludge it may have been treated with polymer before said dewatering to improve a subsequent dewatering. Addition of polymer to the sludge is considered providing a chemically treated sludge which then is dewatered, which provides a chemically treated dewatered sludge. If the incoming sludge is a dewatered sludge it may be provided as a thickened sludge or a sludge cake with fairly high water content.
The incoming sludge, i.e. the sludge of step a) may have a pH of about 6-8.5, such as pH of about 6-8, about 6.5-8, or about 7-8.
Municipal sludge entering the present process may have a pH slightly below 7. Incoming industrial sludge may have a pH slightly above 7.
Sludge Conditioning with Catalyst First
A beaker was provided with 220 g sludge. The sludge was subjected to rapid mixing of about 300 rpm. A calculated amount of catalyst was added, and followed by mixing for 2 min. A calculated amount of HO2 was added to the sludge, and followed by mixing for 5 -10 min. Thereafter the treated sludge was flocculated by addition of different amounts of polymer. The polymer amounts used in the examples are below given as amounts of the polymer products, not as dry solids thereof. The sludge was once again subjected to rapid mixing for about 2-5 s. Once flocs were formed, the mixing was stopped. All the conditioned sludge in the beaker was transferred to a Minipress for dewatering. After the Minipress testing was completed, the obtained the sludge cake was retrieved and measurement of the cake dryness (i.e. solids contents) was made by using heating in an oven over night at 105° C. The standard viscosities of the polymers used have been measured at 0.1 weight-% solids content in an aqueous NaCI solution (1 M), at 25° C., using Brookfield DVII T viscometer with UL adapter.
Undigested sludge from a wastewater treatment plant mainly treating municipal wastewater. The incoming sludge having pH of 6.6 and a solids content of about 3.40-5.32 wt %. The polymer used was a high molecular weight cationic polyacrylamide having a standard viscosity of about 2.7-3.4 mPa·s. The addition amount of polymer stated in the table below relates to polymer product as such, containing 46% total solids content. The addition amount of H2O2 stated in the table below relates to H2O2 product as such, having 50% active agent content.
Ref 1 shows result without H2O2. Examples 2, 3 and 4 clearly show an increase in sludge cake dryness compared to the reference sample.
Undigested sludge from a wastewater treatment plant mainly treating industrial wastewater (mainly printing and dyeing). The incoming sludge having pH of 7.7 and a solids content of 5.62 wt %. The polymer used was a high molecular weight anionic polyacrylamide having a standard viscosity of about 4.7-5.8 mPa·s. The addition amount of polymer stated in the table below relates to polymer product as such, containing 90% total solids content. The addition amount of H2O2 stated in the table below relates to H2O2 product as such, having 50% active agent content.
Ref 5 and 6 shows result without H2O2. Examples 7 and 8 clearly show an increase in sludge cake dryness compared to the reference samples. The dewatering works very well under higher pH.
Dewatered sludge from a centrifuge of a wastewater treatment plant mainly treating industrial wastewater (mainly printing and dyeing). The sludge having a solids content of 22.6 wt %. The sludge is then diluted before conducting the testing. The diluted sludge having a solids content of 4.52 wt % and pH of 7.3. The polymer used was a high molecular weight anionic polyacrylamide having a standard viscosity of about 4.7-5.8 mPa·s. The addition amount of polymer stated in the table below relates to polymer product as such, containing 90% total solids. The addition amount of H2O2 stated in the table below relates to H2O2 product as such, having 50% active agent content.
Ref 9 and 10 shows result without H2O2. Example 11 show an increase in sludge cake dryness compared to the reference samples. The dewatering works very well under higher pH.
Sludge Conditioning with Radical Initiator First
A beaker was provided with 220 g sludge. The sludge was subjected to rapid mixing of about 300 rpm. A calculated amount of radical initiator was added, and followed by mixing for 2 min. A calculated amount of catalyst was added to the sludge, and followed by mixing for 5-10 min. Thereafter the treated sludge was flocculated by addition of different amounts of polymer. The sludge was once again subjected to rapid mixing for about 2-5 s. Once flocs were formed, the mixing was stopped. All the conditioned sludge in the beaker was transferred to a Minipress for dewatering. After the Minipress testing was completed, the obtained the sludge cake was retrieved and measurement of the cake dryness (i.e. solids contents) was made by using heating in an oven over night at 105° C.
Undigested sludge from a wastewater treatment plant mainly treating municipal wastewater. The incoming sludge having pH of 6.6 and a solids content of about 3.40-5.32 wt %. The radical initiator was sodium persulfate (Na2S2O4, SPS). The polymer used was a high molecular weight cationic polyacrylamide having a standard viscosity of about 2.7-3.4 mPa·s. The addition amount of polymer stated in the table below relates to polymer product as such, containing 46% total solids content.
Ref 12 shows result without sodium persulfate. Examples 13-17 clearly show an increase in sludge cake dryness compared to the reference samples.
Undigested sludge from a wastewater treatment plant mainly treating industrial wastewater (mainly printing and dyeing). The sludge having pH of 7.7 and a solids content of 5.62 wt %. The radical initiator was sodium persulfate (Na2S2O4, SPS). The polymer used was a high molecular weight anionic polyacrylamide having a standard viscosity of about 4.7-5.8 mPa·s. The addition amount of polymer stated in the table below relates to polymer product as such, containing 90% total solids content.
Ref 18 and 19 shows result without sodium persulfate. Examples 20 and 21 show an increase in sludge cake dryness compared to corresponding reference sample. The dewatering works very well under higher pH.
Dewatered sludge from a centrifuge of a wastewater treatment plant mainly treating industrial wastewater (mainly printing and dyeing). The sludge having a solids content of 22.6 wt %. The sludge is then diluted before conducting the testing. The diluted sludge having a solids content of 4.52 wt % and pH of 7.3. The radical initiator was sodium persulfate (Na2S2O4, SPS). The polymer used was a high molecular weight anionic polyacrylamide having a standard viscosity of about 4.7-5.8 mPa·s. The addition amount of polymer stated in the table below relates to polymer product as such, containing 90% total solids content.
Ref 22 and 23 shows result without sodium persulfate. Examples 24 and 25 show an increase in sludge cake dryness compared to corresponding reference sample. The dewatering works very well under higher pH.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2017/087993 | 6/13/2017 | WO | 00 |
