Note: Descriptions are shown in the official language in which they were submitted.
~ W094/024~ 21~ ~ ~ S 1 PCT/FI93/00302
Process for purifying sludge contA;n;ng mainly water
This invention relates to a process for purifying sludge
cont~;n;ng mainly water, especially a waste water sludge of
the forest industry, wherein the dewatering properties of
the sludge are improved before carrying out a mechanical
dewatering of the sludge.
Besides the house hold also the industries and, above all,
the forest industry are producing waste water. The paper
production is carried out from a diluted water suspension
wherein water is an auxiliary driving medium.
Waste water contains varying amounts of dissolved and solid
organic and inorganic matter originating from used raw
materials. Waste water thus pollutes the water system to
which it is drained. The solid, insoluble matter makes the
water turbid and forms a layer of sludge on the bottom of
the water system. Organic matter, whether dissolved or
solid, is consuming the oxygen o~ the water system, dyeing
the water and giving directly or indirectly a taste or a
smell to it.
One way to purify waste water is by flocculation. Floc-
culation or coagulation can be enhanced by varying the so-
called zetapotential of the particles contained in the water
by adding suitable chemicals. Because these additions only
influence on the active sites on the solid material, quite
small amounts of the chemicals are usually needed, i.e.
generally 0.1-1 mg/l. If the flocculant has a high molecular
weight, it is simultaneously also functioning as a pro-
tecting colloid.
There is a myriad of flocculants on market. They are water-
soluble but can get hydrolyzed when diluted and form
insoluble solid or colloidal matters, such as e.g. Al(OH) 3 .
W094/0~24 ~ PCT/~193/003
2 1406~ ~ 2
Because flocculants alone or as combined with the particles
generally have an amphoteric nature, i.e. contain groups of
opposite charges, or are salts of bases and acids, they may r
and act both anionically and cationically, according to the
5 pH value of the environment. When both of the amphoteric
groups contribute as much in the molecule or flake conglo-
merate, which requires a certain hydrogen ion concentra-
tion, the isoelectric point of the matter or flake has been
reached. The zetapotential is then near the value of i0mV.
If the flocculant by itself forms flakes, such as e.g.
Al(OH) 3, Fe(OH) 3 and SiO2, the dissolved substances can be
adsorbed to these flakes and thus get separated from the
water to be purified. As an example the absorption of humus
15 and coloring substances to the flakes of Al(OH)3 can be
mentioned.
In the following some usual flocculants are listed:
The resin qlue is mainly Na-abietate. The contribution of it
20 to the zetapotential is negative. Thus its action is anio-
nlc .
The principal factors of alum are the hydrolysis products of
the hexa-aquoall~m;m1m ion with a charge of +3, and the mag-
nitude and the sign of the charge depend on the pH value of
25 the environment. The contribution of alum to the zetapoten-
tial is positive. Thus its action is cationic.
By using both of these and by adjusting the acidity it is
possible to adjust the zetapotential near the value of i0mV
30 and thus to effect flocculation.
The synthetic flocculants can be divided into following
categori~s:
35 Non-ionic polymers, e.g. polyvinyl alcohol, polyethylene
oxide.
~ W094/02424 2 14 D 6 3 1 PCT/Fl93/00302
Ionic polymers, the 80- called polyelectrolytes:
- anionic polymers such as polyacrylate,
polymethacrylate
- cationic polymers such as quaternary
~mmon; um compounds
- copolymers of anionic and cationic groups,
having a protein-like effect.
Copolymers of ionic and non-ionic groups, e.g. partly
saponified polyacrylamide.
In the chemical treatment it is in the first r~lace question
of destabilization (also called coagulation) of a colloidal
suspension, so that the separate particles adhere to each
other and form so large solid particles that these can be
separated from the water by conventional mechanical methods.
Thus it is evident that also a part of the so-called dis-
solved matter is Le,lloved in the chemical treatment.
In the chemical treatment of water usually inorganic salts
are used which form trivalent ions in the water solution.
These include the alnm;n~lm and ferric salts. In chemically
suitable conditions they form in water gelatinous hydroxide
polymer precipitates, flocs.
When a cationic electrolyte is added in th.~ ~resence of a
base so that charged polymerized hydroxide mG'ecules
Me~(OH)y~ are formed, the colloid adsorbs these on its
surface and the zetapotential is lowered. As a zetapotential
m~k; ng the collision and adhering of the particles possible
the values in the range of -5 to +5mV are generally
considered.
Alum flocculates best within the pH range of 4.5 to 7.5.
Because it is by nature an acidic material in a water
solution, an addition of a base is often needed in order to
keep the pH value within the optimal range. Sodium aluminate
W094/02424 PCT/Fl93/003
is basic by nature. The combined use of al-~m and aluminate
can thus give a good result without any adjustment of the pH
with other chemicals.
When alum is added to water with a sufficient basicity
alllm;nllm hydroxide is immediately formed. The molecules
form quickly polymers with linear ch~;n~ and of an order of
magnitude lOnm. This is observed as a turbidity. The hydro-
xide polymers are ; mmP~; ~ tely absorbed on the negatively
charged surface of the colloidal particle, and cover it. If
there are no impurity particles present, the hydroxide po-
lymers form flocs with each other. This is of course inef-
ficient in respect of the water purification.
The precipitates formed with the aid of alu~ and iron salts,
in the following flocs, can be small and they disintegrate
quite easily. The activated silicic acid is reinforcing
them; the same result is sought by the addition of long-
chain polyelectrolyte chemicals, flocculating aids. Gene-
rally the main purpose of this, however, is to gather up thewidely scattered and small flocs and to reduce their speci-
fic surface, thus increasing the se~;m~ntation rate of the
solid particles.
The destabilization of the colloids can also be carried out
by adding cationic polyelectrolytes to the water to be
treated. These bring the system to the isoelectrical point
without any pH change. Albeit such polymers are as coagu-
lants 10 to 15 times more effective as alum, they still are
clearly more expensive for thi purpose. Therefore they are
mainly used in very small quantities e.g. to enhance primary
flocculation especially with alum.
The polyelectrolytes which are used as an flocculating aid,
are generally classified according to their origin (natural
or synthetic) and their ionic nature (cationic, anionic,
non-ionic or copolymers). To mention examples, starch is
W094/02424 2 ~ 4 0 6 3 1 PCT/Fl93/00302
natural and cationic polyacrylic acid as well as anionic
polyacrylic amide are synthetic. The molecular weights vary
between 15 000 to 15 000 000 and the lengths between about
5 000 to 20 OOOnm.
FI Patent Application No. 890533 presents ~ process for
treatment of waste water by adding a) an inorganic pre-
cipitant, b) an anionic polymer and c) a cationic polymer to
the waste water. The treatment, i.e. the order of addition
represents in this patent application a part of the inven-
tion.
FI Patent Application No. 830492 presents an invention for
forming a filter cake with such chemicals which enhance
separation of solid and liquid phases. According to the
application, a polyelectrolyte having a high molecular
weight is first added, and finally an inorganic matter or a
polyelectrolyte having a small molecular weight.
The present invention expressly concerns an improvement by
which the separation of solid matter from a ~ludge is made
more effective, especially from the waste water sludge of
the forest industry, by a combination of a coagulant of a
suitable type and polymeric chemicals.
In the forest industry, as a result of the biological puri-
fication of waste water a sludge surplus is formed which is
usually treated together with fibre or bark sludges. The
most common way is to mix the sludges together, condition
with an organic polyelectrolyte, remove water mechanically
e.g. with a filter belt press and dispose of the dried
(= water has been mechanically removed) sludge by burning.
The separation of water from the biosludge is very diffi-
cult, and often the situation is hampered by the fact that
the portion of the biosludge in the mixture to be treated is
varyingO In that case the importance of the c~,nditioning
~ ~ 4 ~ 6 PCT/FI93/0030~
chemical which is added before the mechanical dewatering
stage i5 further ~mp~ized.
In Finland it is also common to use a (poly)ferric sulphate
or polyaluminium chloride together with a polyelectrolyte,
so that this inorganic coagulant is added first, and at a
later stage the polyelectrolyte. By this way a better drying
result can be obtained and save in the chemical costs.
There are also publications concerning the addition of
ferric sulphate and a cationic polyelectrolyt: at different
mom~ntS in the conditioning of forest industry sludges
[Tappi J. 1985, Chem. Eng. 1985].
According to the patents JP-893088253 and JP-02180700 the
treatment of an organic sludge with ferric or alllm;nllm
chemicals together with an amphoteric polymer (= a mixture
of different types) will improve the separation of water
from the sludge and make it more easy to remove the sludge
cake from the filter cloth. The chemical consumption is also
decreased.
Mixtures of an inorganic coagulant and an organic polymer
have been used, for instance, tO removing turbidity of waste
water, but not together with a polyelectro~ e which is
added separately [US-4 902 779, US-5 035 808]. Neither are
there any applications to be found on the treatment of the
forest industry sludges with a system of a coagulant mixture
+ a polyelectrolyte.
The goal of the invention is to provide a process for
purification of a sludge cont~;n'ng mainly water, especially
a forest industry waste water sludge, by enhancing the dewa-
tering properties of the sludge, which will further facili-
tate and increase the efficiency of the subse~uent mechani-
cal dewatering.
W094/02424 21 ~ 0 6 31 PCT/Fl93/00302
The main characteristics of the invention appear from the
appended patent claims.
According to the invention, it has surprisingly been obser-
ved that when in the first addition step (a) instead of aferric salt a mixture is u~ed wherein to the ferric salt an
organic polymer with a molecular weight under 1 million is
added, the amount of the organic polyelectrolyte having a
molecular weight above 3 million and which is added in the
second addition step (b), can be reduced without impairing
the dewatering properties of the sludge. It ha~ according to
the invention also been observed that if the amount of this
polyelectrolyte is not reduced, the dewatering properties of
the sludge are improved.
The ferric salt of the coagulant mixture which is used ac-
cording to the invention, is preferably ferric sulphate
and/or polyferric sulphate. This coagulant mixture is pre-
ferably fonmed of a mixture of a water solution of the
ferric salt and a water solution of an organic polymer. The
water ~olution of the ferric salt contains preferably about
12 percent by weight ferric salt.
The coagulating mixture contains ferric salt and an organic
polymer preferably at a ratio of 1:0.01 to 1:0.33.
Said organic polymer is preferably poly(dimethyl diallyl
~mmo~; um chloride) and/or polyep; ~m; ne .
Said polyelectrolyte is preferably cationic, anionic or non-
ionic polyacrylamide and/or an polyamine.
r
In the following the invention is described in more detail
with Examples with reference to the appended drawings,
wherein
Fig. 1 is a graphical presentation of the correlation
W094/0~ ~ ~ PCT/FI93/003
between the dry solids and CST, and
Figs. 2-4 are graphical presentations of the results
obt~;ne~ with the reference tests described in
the Examples.
The water separability from the sludge is described by the
obt~;n~hle dry solids content of the cake, also with the CST
(capillary suction time) value: the lower the CST value is,
the more easily the water is separable from the sludge. It
has to be noted that low CST values are also reached with
overdoses of the polyelectrolyte, but then the water sepa-
ration is not necessarily good. The correlation between the
dry solids content and CST is represented by the curve of in
Fig. 1.
There is a correlation between CST and the dry solids con-
tent: when CST decreases the dry solids content increases.
Thus the CST is a very rapid method for a rough comparison
of chemicals and estimation of chemical do~age.
The precentages given in the following Examples are by
weight.
Example 1
In this example a sludge mixture from a forest industrial
plant was used which cont~;ne~ 40~ biosludge calculated from
the dry solids content and the dry solids content of which
was 1,4 ~. At the first stage a coagulating mixture accor-
ding to the invention was used instead of polyferric sulp-
hate (reference) and at the later addition stage the amountof the polyelectrolyte was reduced. The used polyelectrolyte
was a cationic polyacrylamide ~trade name Millfloc Q39).
The coagulating mixtures were mixtures of Folyferric sulp-
hate PFS (12~ water solution), and polydimet~l diallyl
~mmon;um chloride (40~ water solution), in short the polymer
or p-DMDACo The weight ratios of the polyferric suphate and
~ WO9~/0~4~ 21 ~ ~ ~ 3 ~ PCT/Fl93/0030~
the polymer in the coagulating mixture were the following:
PFS p-DMDAC
Coagulating mixture 1 1 : 0,13
Coagulating mixture 2 1 : 0,016
The reference test was carried out by using only PFS at the
first stage. The coagulant dosage was 113mg/g of dry solids
of the sludge mixture in all chemical adding methods.
The results are presented in Fig. 2 so that the reference
test is (a), the coagulating mixture 1 is (b), and the coa-
gulating mixture 2 is (c). According to the results the
amount of the polyelectrolyte to be added at the second
stage per dry solids (the horizontal axis of Fig. 2) can
clearly be reduced without ;mr~lring the final result when,
at the first stage, the coagulating mixture according to the
invention is used. On the other hand, when only PFS is used,
the dewatering result is uneven and occasionally very poor.
Example 2
In this example the starting situation was that the sludge
mixture with a dry solids content of 1,5 ~ was from another
forest industrial plant and contained 40 ~ f,urplus sludge
from an active sludge plant and 60~ fibre sl~d~e.
In the reference test polyferric sulphate (PFS) was used at
the first stage as a water solution having a Fe-content of
12~.
For the tests the coagulant mixtures 3 and 4 were prepared,
which were composed of the above mentioned PFS and the po-
lymeric p-DMDAC according to Example 1. The weight ratios of
the coagulant mixtures were as follows:
W094/0~24 ~ PCT/FI93/003~
PFS p-DMDAC
Coagulant mixture 3 1 : 0,02
Coagulant mixture 4 1 : 0,03
When conditioning with any of the three chemical addition
ways the same polyelectrolyte dosage, which was lmg/g, was
used after the above mentioned dosage. The polyelectrolyte
was a cationic polyacrylamide as a 0.5~ water solution. The
trade name of the polyelectrolyte is Fennopol K1351 and its
molecular weight was over 3xl06.
The results are presented in Fig. 3, where the result of the
reference test is (A), the result obtained with the result
coagulant mixture 3 is (B), and the result -~ith the coagu-
lant mixture 4 is (C). From the Figure it car ~e seen, thatwhen the coagulant mixtures 3 and 4 are used, a higher
sludge dry solids content is obtained than with only PFS,
when the polyelectrolyte dosage with all three is the same.
An essential improvement can be obt~;ne~ especially with
relatively high PFS dosages.
Example 3
In this example a sludge mixture of a third plant was used,
which sludge contained less biosludge than in the previous
examples, only 4~ of the dry solids.
As a reference coagulant PFS (12~ water solution) was used
and as the coagulants according to the invention the follo-
wing mixtures of PFS and p-DMDAC (40~ wate solution) with
the following weight ratios:
PFSThe polymer
Coagulant mixture 5 i :0,18
Coagulant mixture 6 1 :0,25
Coagulant mixture 7 1 :0,33
The dosage of the coagulant mixture was 10-15 mg/g of the
2i~0631
W094/0~ ~ PCT/Fl93/00302
11
dry solids. As the polyelectrolyte after the dosage of the
coagulant a 0.5~ water solution of polyacrylamide was used.
The trade name of the polyelectrolyte is Fennopol K504.
The results are presented in Fig. 4, wherein the reference
test is (I), so that the result I~ was obtA;neA with the
dosage of lOmg/g and the result Ib was obt~;ne~ with the
dosage of 15mg/g. The result of the coagulant mixture 5 is
(II~, wherein the dosage was lOmg/g. With the coagulant
mixture 6 the results III~ and IIIb were obtained, corres-
ponding the dosages of lOmg/g and 14mg/g. The coagulant
mixture 7 is (IV) and the dosage was 10 mg/g.
From the Figure it can be seen that increasing the amount of
both PFS and the organic polymer m; ~e~ to PFS essentially
improves the dewatering properties of the sludge, i.e. the
CST value is reduced. The amount of the polyelectrolyte can
thus be reduced considerably.
.. . .
