CA2185127A1 - Waste treatment agent - Google Patents
Waste treatment agentInfo
- Publication number
- CA2185127A1 CA2185127A1 CA002185127A CA2185127A CA2185127A1 CA 2185127 A1 CA2185127 A1 CA 2185127A1 CA 002185127 A CA002185127 A CA 002185127A CA 2185127 A CA2185127 A CA 2185127A CA 2185127 A1 CA2185127 A1 CA 2185127A1
- Authority
- CA
- Canada
- Prior art keywords
- compound
- mineral
- alumino
- zeolite
- activated
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Sludge (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention is directed to the treatment of waste water and other polluted materials. A compound of the general formula:
(ZO)nAln(OH)n-mClm (or of closely related empirical formula), wherein Z is derived from an aluminosilicate material, is prepared by activating the aluminosilicate material by treating with acid or by subjecting the material to ammonium ion exchange and then heating the thus activated material in the presence of an alumino compound. The preferred aluminosilicate is a zeolite-containing mineral of a clinoptilolite structure and the preferred alumino compound is polyaluminiumchloride. The resultant product is pH neutral; non-toxic;
suitable for use in flotation and sedimentation tanks, destabilizes suspensions, dispersions and emulsions; can be used over a wide pH range;
is amphoteric and particularly suited for the elimination of heavy metal cations and phosphate anions; reduces chemical oxygen deficiency, biological oxygen deficiency and adsorbable organic halogenated hydrocarbons; decreases the amount of sludge while simultaneously increasing dry matter content; does not swell; is economical to use; and is not harmful to the environment.
(ZO)nAln(OH)n-mClm (or of closely related empirical formula), wherein Z is derived from an aluminosilicate material, is prepared by activating the aluminosilicate material by treating with acid or by subjecting the material to ammonium ion exchange and then heating the thus activated material in the presence of an alumino compound. The preferred aluminosilicate is a zeolite-containing mineral of a clinoptilolite structure and the preferred alumino compound is polyaluminiumchloride. The resultant product is pH neutral; non-toxic;
suitable for use in flotation and sedimentation tanks, destabilizes suspensions, dispersions and emulsions; can be used over a wide pH range;
is amphoteric and particularly suited for the elimination of heavy metal cations and phosphate anions; reduces chemical oxygen deficiency, biological oxygen deficiency and adsorbable organic halogenated hydrocarbons; decreases the amount of sludge while simultaneously increasing dry matter content; does not swell; is economical to use; and is not harmful to the environment.
Description
~ WO 9~!i/2~21j~ 2 ~ 8 5 1 2 7 PCT/AU~/00122 FIELD OF TF[E INVENTION
THIS INVENTION relates to the treatment of waste water and other polluted materials. In particular, it is directed to the production and use of a '_ _ Ullll which ef f iciently clarif ies or otherwise treats these waste materials.
BACRGRO~IND OF T~E lNV~ . lON
Today it is a requirement of most Government Authorities that polluted waters and other waste materials are adequately treated before their use and/or tl; ero~l This is of particular concern when conditioning water f or drinking purposes and when treating ef f luent generated by industry . For example, a number of industries produce harmful by-products which must be disposed of carefully without undue harm to the environment.
It is a complex task to purify polluted water because the pollutants have quite dif ferent properties, part;mll~tC~ sizes and reactivities;
they may appear in solution, in colloid form, as a sl1cp~nC;nn, dispersion or aerosol, in small or large particulate size.
Traditionally, treatment of these waste waters is a multi-stage process requiring separate screening, se~ ation, filtering and other tanks where the undesirable ~ __ ~ Ls are eliminated by ion exchange, precipitation, f locking, f iltration;
centrifugation, oxidization or reduction, osmosis, 2~ 8~1 27 Wo 9~I2~266 PCT/AU95/00l22 electrolysis etc., as well as biological removal using microorganisms.
As waste water can contain many pollutants-cations such as ammonium or heavy metals, anions such as phosphates and sulphates, hydrocarbons, fats, proteins and caLb~l.y~ es etc. - several or all of the above processes are required and it is not Ul: for ten (10) separate stages to be undertaken to meet the required water quality standards.
When treating such waste materials, cr~nc~ ration must be given to the choice of agents to be used as these agents themselves, and the products resulting f rom their use, must also not have a detrimental impact on the environment.
Conventional products f or water treatment are usually iron, A~ ; n; or calcium c . u--ds which induce precipitation and f locking. Such inorganic coagulants have long been used as an agent f or treating polluted water. ~uch research has been undertaken to improve the ef f iciency of these agents. For example, polyiil n; -hl~ride is a f avoured coagulant in se~ i ation tanks and in a method described in Japanese Un~Y~ nf~fl Patent Publication No 60-209214 (Application No 59-65078, filed April 3, 1984) it is blended with finely divided ~1 noC; l; t-ate-containing minerals tQ
provide a means f or improving the time taken f or sedimentation to be effected.
However, even this i _~Jved se~l; tation process is but one step in the many stages usually re~ired ~ WO 95124266 2 1 8 5 1 2 7 PCT/AU9.i~0012~
to adequately treat waste water and research has continued to develop new methods which have f ewer stages, reduce sludge ciuantity and/or make it pn~c:;hlt~ to reuse the sludge as a raw material in some other application. Purther, research is continuing to develop more ef f ective reagents to render the water treatment process more e r~ l ~
For example, the above-described Japanese process has been further i uv~:d and is described in Japanese lln~mi nPd Patent Publication No 3-056104 (Application No 1-192232, filed July 25 1989). In one : '; t of this improved prior process, separate quantities of an Al int s:; licate mineral, particularly one containing a zeolite, are individually treated with ( 1 ) sulphuric acid to give a product "a", ( 2 ) with hydrochloric acid followed by poly;3l n; lt ride to give a product "b", and ( 3 ) with sodium hydroxide to give a product "c". The products a, b and c are then blended together in a 1:1:1 ratio to give a mixture which is then used to clarify rol l lltPA
water .
While this; uv~d process may be 5llrc~ssful, it would appear to be ( 1 ) less ec~nt f'~l than the previous L)r ucesses as it requires three separate ^nts to be prepared bef ore the actual clarification agent can be prepared, leading to higher costs of raw materials and longer production times; and ( 2 ) the negative charge of the skeleton of product "b" limits its effectiveness in a cation/anion environment.
21 ~5127 Wo 9~2~266 PCr/A~ss/0012z It is an object of the present invention to eliminate, or at least ameliorate, one or more of the above problems and to provide an agent f or the treatment of waste water and other polluted materials which is e~: irAl to produce, effective in the removal of more than one type of pollutant and which is environmentally f riendly .
SUMMARY OF TE~E INVENTION
It has now been es~Ahl; Sh~d that by first activating an AlllminnRil;cate material and then hl~nA; n~ with an alumino ~ _ ' followed by the application of a heat produces an agent which meets these ob j ectives .
Therefore, according to a first aspect of the present invention, there is provided an aqent for the treatment of waste water and o~her polluted materials, said agent comprising a ~~ ' of the general formula:
( ZO ) nAlr, ~ OH ~ n_mClm or a ~_ __ ' of closely related empirical formula, wherein Z is derived from an Alllm;nnsil;r/tF.
material .
As a second aspect of the present invention there is provided a method for the preparation of a ' of the general formula:
( Z ) nAln ( OEI ) n -mClm w09s~24266 2 1 8 5 1 2 7 PcTMUg~al22 or a _ ' of closely related empirical formula, wherein Z is derived from an al~minnc;l;n~te material, said method comprising:
1~ activating said material; and 2 ) heating the thus activated material in the ~lesel~ce of an alumino ~ '.
A third aspect of the present invention is a method of purifying waste water and the like, said method comprising treating the waste water and the like with a c~ - ' having the f ollowing general f ormula:
( zo ) "Al,~ ( 0~ mClm or a ~ d of closely related empirical formula, wherein Z is derived from an ~ minnc;l;cate material .
The all ; nnC; l; cate can be a natural or synthetic material .
Preferaoly, the material is a zeolite-containing mineral.
Preferably, the zeolite content of the mineral is 40 to 95% by weight.
Preferably, the Si:Al ratio of the zeolite is greater than 3.
Wo 9~/2l~266 PCT/A~g~/00122 More preferably, the zeolite is of a clinoptilolite structure .
Most preferably, the mineral is finely divided to a particle size of 250 microns or less.
Pref erably the zeolite-containing mineral is activated by treating with acid or by subjecting said mineral to i l~m ion ~ h~n~e.
2iore preferably, the zeolite-cr~nt~;nin~ mineral is activated by treatment with hydrochloric acid.
Preferably, the alumino ~ _ulld is a poly.ql ni salt .
More preferably, the poly~l ini salt is poly~1 niI 1~ ride.
Preferably, the ratio of mineral: alumino c _ulld is in the range of 1: 0 . 01 to 1: 2 by weight.
More pref erably, the ratio is 1:1 by weight .
Preferably, the activated mineral and the alumino ,_ _ ~ are heated together at a t ~ LUL t: which is in the range 100 - 600C.
20More preferably, the heating is undertaken at 300 ~C .
Preferably, the product of the invention is granulated to a particle size of 0 . 25 - 100 mm.
~ wo gsl24266 2 1 8 5 1 2 7 PCTlAU9~ 112~
It is important to appreciate that the product of the present invention is different from product "b"
ref erred to above with ref erence to the Japanese Un~m;n~-d Patent Publication No 3-056104. In the prior process, a mere admixture is f ormed, not a new and ~h~m; C;l 1 1 y distinct ~_ _ u.-d as in the present invention. Further, the prior process only applies sufficient heat to achieve drying of the product. Typical drying temperatures are in the range 40 to 60C - any higher, and the polyaluminiumchloride begins to A~ -~ and lose its ef f ectiveness .
In contrast, the present invention generally applies heat at a much higher temperature but for a si~n; f; ~ntly shorter duration and in a manner which avoids signif icant decomposition of pOlyAl n; ,1 nride to form a completely new product .
DESCRIPlION OF T~E INVENTION
OENl~RAL EXZ~E
A naturally occurring, acid-resistant, thP ~able, zeolite-containing mineral is f irst f inely divided by any convenient means and then activated by washing with hydrochloric acid. An agueous poly~l- ni - '-lnride solution is then added and the mixture is heated between 150 and 250 C with simultaneous evaporation of water. The product is then cooled relatively rapidly by passing through a spray tower.
wo 9s~24266 pcTlAllsslool22 The product formed preferably has a water content of less than lO percent by weight, more preferably less than 5 percent by weight.
Although not wishing to be bound by theory, the reaction is believed to be a dehydroxylisation between the protonated zeolite and the hydroxyl groups of partially hydrolized poly;ll in;1lm chloride .
In more detail, referring to the ~t nying drawing, a mixture of a finely divided zeolite-containing mineral and an aqueous poly~1 'ni ~ lnride st~ t;nn cnntA;ning 30 to 70 weight percent poly~1 n; -hlnride iS mixed in a container l, and acidified with hydrochloric acid to a pH of at least l. 5 . The mixture is fed to the upper end of a spray tower 4 via line 3 provided with a pump 2. Alternatively, these c ^nts can be fed separately to the top of the tower. The tower height is in the range of about lO to 30 metres. For a~: ~;ntJ the mixture, a rotating disk 5 is provided at the top of the tower 4. From its upper to lower end, hot air is passed through the spray tower 4, as shown by arrows 6.
The temperature of the air stream 6 is not more 25than 250C, preferably not more than 200C. If the temperature is significantly higher, the polyaluminiumchloride tends to tle - - to alumini, ` ydLu~side or aluminiumoxide before the zeolite can react.
The composite product formed leaves the base of the tower 4 in solid form, as shown by arrow 7. During the passage, the water produced by the reaction 2~85127 ~ WO 95124~66 PCT/AlJgS/llOlZ2 evaporates ~ arrow 8 l . Due to this evaporation, the temperature of the air stream 6 decreases constantly. That is, the solid composite product 7, leaving the base of the tower 4 has a temperature of less than 100C, preferably less than 90C.
The rF~q; ~l~nt-e time of the mixture in tower 4 is between 2 and 10 minutes.
The product of the present invention is believed to be of the general formula (Z-O~r,Alr,~OE~ m(Cl)m, wherein m is greater than 0. However, it is dif f icult to provide an exact empirical f ormula because the product of the invention can exist in various forms. Three P 1PS: of these forms are given below:
\
Al - OH Al - OH Al - Cl 20 Z - O Z - O Z - o \
Al - OH Al - OH Al - Cl /
Z - O Z - O Z -- O
Al - OH Al - Cl Al - OH
/
Z - O . Z - O Z - O
30 Al - Cl Al - OH
Modif ications to this general example are p~ ; hl P .
For example, the mixture of activated zeolite and aqueous pOlyAl 'n; ' l~ride can first be dried at less than 100C (to avoid ~1P_ __-;n~ the polyal, ;n; ' l~lride) and under vacuum if that is W~ ~'i12~2G6 PCTIAU~5/OUl22 deemed necessary to further reduce the likelihood of the polyaluminil hlnride tlf- _~~;n~, and then the mixture is heated between 250 and 600C.
The product of the invention is usually used at the 5 rate of 0.1 g to 10 g/l of waste water, more particularly, O . 2 to O . 5 g/1 of waste water .
SPECIFIC
Example 1 A mineral containing about 60 weight percent of clinoptilolite and having a grain size of not more than 250 micron is mixed in a weight ratio of 1: 1 with an af~ueous polyA~ ;n; ' lnride solution having a polyaluminiumchloride content of about 50 weight percent. To this mixture is added hydrochloric acid, until a p~l of less than 1. 5 is obtained. The mixture is fed to the top of the spray tower where it is atomized by the rotating disk. Air at a temperature of 150 to 200C is fed to the top of the spray tower. The rPc;cl~onre time 2 0 of the mixture in the tower is about 3 to 5 minutes. The solid composite product leaves the tower at a temperature of about 90 to 95C with a water content of about 2 to 5 weight percent.
Example 2 Waste water was used from an optical plant and contained a large amount of hydrorA rbon c, a high value of rhPm; rAl oxygen d~fir; Pnry and a signif icant quantity of heavy metal ions, such as zinc and nickel.
~ WO95124266 2 1 ~ 5 ~ 27 PCT/AU!?5/00122 The product of the invention was prepared in accordance with Example 1 aoove and the waste water was treated with the following ~ ~lds for cornparison:
A ) A1 z ( 5O4 ), Aluminiumsulf ate B) Zeolite + Alz(SO4)3 mixed 1: 1 C ) Zeolite + PAC mixed ( PAC = Poly;l 1 n; ~ 1 nride ) D) Product according to Example 1 All analyses were conducted according to the German standard DIN.
o ~c A-D were tested at 1 g/1 of waste water and the pH adjusted to 8 with Ca(OE~) z .
Af ter addition of the product, the waste water was stirred at 500 rpm at 18 to 20C for 10 minutes.
The resultant precipitate was separated by filtration using a paper filter. The filtration rate was measured.
The determination of the heavy metal ion content was perf ormed with an atomic absorption spe~, LL ~ ~L .
The results are shown in Table I.
21 ~5 1 27 O O ~ u~ ~ _I O O ~ ~I' O ~D ~1 0 0 0 0 ~n ~D r1 O ~ t V V V Irl a ~
o o O
O O Lr) ~D ~ ~ O, o ~D ~D O O O o .) ~ rt ~.) ~1 ~rl O O ~7 N a. ~O O O O
O N ~ m r o o ~ ~r ~D " O O
m c , J U7 - o o m o ~ N ~t ' O ' O N 1'7 N ~i 0 0 0 0 O O ~ U~ ~ O o O
rt = E N r~ ~ E ~ r = æ
SUBSTITUTE SHEET (RULE 26) Wo 9s~24266 2 1 ~ 5 ~ 2 7 rCT/~U9~/00122 Example 3 Waste water from a bath for degreasing and - phosphating metal was used. Products A-D were tested at 5 g/ 1 of waste water .
In all other respects, the same conditions and mea:.uL~ ~s were undertaken as in Example 2.
The results are shown in Table II.
The product of the invention is multi-functional.
Due to the presence of anionic oxygen, it can act as an ion ~ h~n~ r to absorb, for example, heavy metal cations; as it is partly protonated, it can exchange those protons to appropriately proton-acceptable groups such as those f ound in dyes; the ~ mini ~ lnride groups can split off chloride anions thus exhibiting cationic properties to enable the removal of, f or example, phosphate anions.
Importantly, by varying the degree of activation of the ~ rni nnci l i ~atF~ L and the ratio of polyaluminiumchloride, these multi-functional properties can be adjusted to suit the waste material being heated.
By using the present invention, clarification of waste water and other })nl 1 I~t~d materials can be achieved more effectively than prior pLocesses and of f ers at least the f nl 1 owi n~ advantages:
- it is pH neutral;
wo9~cl24266 2~ 851 27 Pcr~Auss/00122 ~
- it is not toxic;
- it is suitable for use in flotation and R~ ation tanks;
- it des~Ahl;7~R sl~C~nc;ons~ dispersions and 5 emulsions;
- the only anion present is hydroxyl;
- it can be used over a wide pH range;
- it is amphoteric and particularly suited for the elimination of heavy metal cations and phosphate anions;
- it reduces chemical oxygen deficiency, biological oxygen def iciency and adsorbable organic h~ on~ted hydrocarbons;
- it decreases the amount of sludge while simult~n~ouRly increasing dry matter content;
- it does not swell;
- it is ec~nl i r;ll; and - is not harmful to the environment.
THIS INVENTION relates to the treatment of waste water and other polluted materials. In particular, it is directed to the production and use of a '_ _ Ullll which ef f iciently clarif ies or otherwise treats these waste materials.
BACRGRO~IND OF T~E lNV~ . lON
Today it is a requirement of most Government Authorities that polluted waters and other waste materials are adequately treated before their use and/or tl; ero~l This is of particular concern when conditioning water f or drinking purposes and when treating ef f luent generated by industry . For example, a number of industries produce harmful by-products which must be disposed of carefully without undue harm to the environment.
It is a complex task to purify polluted water because the pollutants have quite dif ferent properties, part;mll~tC~ sizes and reactivities;
they may appear in solution, in colloid form, as a sl1cp~nC;nn, dispersion or aerosol, in small or large particulate size.
Traditionally, treatment of these waste waters is a multi-stage process requiring separate screening, se~ ation, filtering and other tanks where the undesirable ~ __ ~ Ls are eliminated by ion exchange, precipitation, f locking, f iltration;
centrifugation, oxidization or reduction, osmosis, 2~ 8~1 27 Wo 9~I2~266 PCT/AU95/00l22 electrolysis etc., as well as biological removal using microorganisms.
As waste water can contain many pollutants-cations such as ammonium or heavy metals, anions such as phosphates and sulphates, hydrocarbons, fats, proteins and caLb~l.y~ es etc. - several or all of the above processes are required and it is not Ul: for ten (10) separate stages to be undertaken to meet the required water quality standards.
When treating such waste materials, cr~nc~ ration must be given to the choice of agents to be used as these agents themselves, and the products resulting f rom their use, must also not have a detrimental impact on the environment.
Conventional products f or water treatment are usually iron, A~ ; n; or calcium c . u--ds which induce precipitation and f locking. Such inorganic coagulants have long been used as an agent f or treating polluted water. ~uch research has been undertaken to improve the ef f iciency of these agents. For example, polyiil n; -hl~ride is a f avoured coagulant in se~ i ation tanks and in a method described in Japanese Un~Y~ nf~fl Patent Publication No 60-209214 (Application No 59-65078, filed April 3, 1984) it is blended with finely divided ~1 noC; l; t-ate-containing minerals tQ
provide a means f or improving the time taken f or sedimentation to be effected.
However, even this i _~Jved se~l; tation process is but one step in the many stages usually re~ired ~ WO 95124266 2 1 8 5 1 2 7 PCT/AU9.i~0012~
to adequately treat waste water and research has continued to develop new methods which have f ewer stages, reduce sludge ciuantity and/or make it pn~c:;hlt~ to reuse the sludge as a raw material in some other application. Purther, research is continuing to develop more ef f ective reagents to render the water treatment process more e r~ l ~
For example, the above-described Japanese process has been further i uv~:d and is described in Japanese lln~mi nPd Patent Publication No 3-056104 (Application No 1-192232, filed July 25 1989). In one : '; t of this improved prior process, separate quantities of an Al int s:; licate mineral, particularly one containing a zeolite, are individually treated with ( 1 ) sulphuric acid to give a product "a", ( 2 ) with hydrochloric acid followed by poly;3l n; lt ride to give a product "b", and ( 3 ) with sodium hydroxide to give a product "c". The products a, b and c are then blended together in a 1:1:1 ratio to give a mixture which is then used to clarify rol l lltPA
water .
While this; uv~d process may be 5llrc~ssful, it would appear to be ( 1 ) less ec~nt f'~l than the previous L)r ucesses as it requires three separate ^nts to be prepared bef ore the actual clarification agent can be prepared, leading to higher costs of raw materials and longer production times; and ( 2 ) the negative charge of the skeleton of product "b" limits its effectiveness in a cation/anion environment.
21 ~5127 Wo 9~2~266 PCr/A~ss/0012z It is an object of the present invention to eliminate, or at least ameliorate, one or more of the above problems and to provide an agent f or the treatment of waste water and other polluted materials which is e~: irAl to produce, effective in the removal of more than one type of pollutant and which is environmentally f riendly .
SUMMARY OF TE~E INVENTION
It has now been es~Ahl; Sh~d that by first activating an AlllminnRil;cate material and then hl~nA; n~ with an alumino ~ _ ' followed by the application of a heat produces an agent which meets these ob j ectives .
Therefore, according to a first aspect of the present invention, there is provided an aqent for the treatment of waste water and o~her polluted materials, said agent comprising a ~~ ' of the general formula:
( ZO ) nAlr, ~ OH ~ n_mClm or a ~_ __ ' of closely related empirical formula, wherein Z is derived from an Alllm;nnsil;r/tF.
material .
As a second aspect of the present invention there is provided a method for the preparation of a ' of the general formula:
( Z ) nAln ( OEI ) n -mClm w09s~24266 2 1 8 5 1 2 7 PcTMUg~al22 or a _ ' of closely related empirical formula, wherein Z is derived from an al~minnc;l;n~te material, said method comprising:
1~ activating said material; and 2 ) heating the thus activated material in the ~lesel~ce of an alumino ~ '.
A third aspect of the present invention is a method of purifying waste water and the like, said method comprising treating the waste water and the like with a c~ - ' having the f ollowing general f ormula:
( zo ) "Al,~ ( 0~ mClm or a ~ d of closely related empirical formula, wherein Z is derived from an ~ minnc;l;cate material .
The all ; nnC; l; cate can be a natural or synthetic material .
Preferaoly, the material is a zeolite-containing mineral.
Preferably, the zeolite content of the mineral is 40 to 95% by weight.
Preferably, the Si:Al ratio of the zeolite is greater than 3.
Wo 9~/2l~266 PCT/A~g~/00122 More preferably, the zeolite is of a clinoptilolite structure .
Most preferably, the mineral is finely divided to a particle size of 250 microns or less.
Pref erably the zeolite-containing mineral is activated by treating with acid or by subjecting said mineral to i l~m ion ~ h~n~e.
2iore preferably, the zeolite-cr~nt~;nin~ mineral is activated by treatment with hydrochloric acid.
Preferably, the alumino ~ _ulld is a poly.ql ni salt .
More preferably, the poly~l ini salt is poly~1 niI 1~ ride.
Preferably, the ratio of mineral: alumino c _ulld is in the range of 1: 0 . 01 to 1: 2 by weight.
More pref erably, the ratio is 1:1 by weight .
Preferably, the activated mineral and the alumino ,_ _ ~ are heated together at a t ~ LUL t: which is in the range 100 - 600C.
20More preferably, the heating is undertaken at 300 ~C .
Preferably, the product of the invention is granulated to a particle size of 0 . 25 - 100 mm.
~ wo gsl24266 2 1 8 5 1 2 7 PCTlAU9~ 112~
It is important to appreciate that the product of the present invention is different from product "b"
ref erred to above with ref erence to the Japanese Un~m;n~-d Patent Publication No 3-056104. In the prior process, a mere admixture is f ormed, not a new and ~h~m; C;l 1 1 y distinct ~_ _ u.-d as in the present invention. Further, the prior process only applies sufficient heat to achieve drying of the product. Typical drying temperatures are in the range 40 to 60C - any higher, and the polyaluminiumchloride begins to A~ -~ and lose its ef f ectiveness .
In contrast, the present invention generally applies heat at a much higher temperature but for a si~n; f; ~ntly shorter duration and in a manner which avoids signif icant decomposition of pOlyAl n; ,1 nride to form a completely new product .
DESCRIPlION OF T~E INVENTION
OENl~RAL EXZ~E
A naturally occurring, acid-resistant, thP ~able, zeolite-containing mineral is f irst f inely divided by any convenient means and then activated by washing with hydrochloric acid. An agueous poly~l- ni - '-lnride solution is then added and the mixture is heated between 150 and 250 C with simultaneous evaporation of water. The product is then cooled relatively rapidly by passing through a spray tower.
wo 9s~24266 pcTlAllsslool22 The product formed preferably has a water content of less than lO percent by weight, more preferably less than 5 percent by weight.
Although not wishing to be bound by theory, the reaction is believed to be a dehydroxylisation between the protonated zeolite and the hydroxyl groups of partially hydrolized poly;ll in;1lm chloride .
In more detail, referring to the ~t nying drawing, a mixture of a finely divided zeolite-containing mineral and an aqueous poly~1 'ni ~ lnride st~ t;nn cnntA;ning 30 to 70 weight percent poly~1 n; -hlnride iS mixed in a container l, and acidified with hydrochloric acid to a pH of at least l. 5 . The mixture is fed to the upper end of a spray tower 4 via line 3 provided with a pump 2. Alternatively, these c ^nts can be fed separately to the top of the tower. The tower height is in the range of about lO to 30 metres. For a~: ~;ntJ the mixture, a rotating disk 5 is provided at the top of the tower 4. From its upper to lower end, hot air is passed through the spray tower 4, as shown by arrows 6.
The temperature of the air stream 6 is not more 25than 250C, preferably not more than 200C. If the temperature is significantly higher, the polyaluminiumchloride tends to tle - - to alumini, ` ydLu~side or aluminiumoxide before the zeolite can react.
The composite product formed leaves the base of the tower 4 in solid form, as shown by arrow 7. During the passage, the water produced by the reaction 2~85127 ~ WO 95124~66 PCT/AlJgS/llOlZ2 evaporates ~ arrow 8 l . Due to this evaporation, the temperature of the air stream 6 decreases constantly. That is, the solid composite product 7, leaving the base of the tower 4 has a temperature of less than 100C, preferably less than 90C.
The rF~q; ~l~nt-e time of the mixture in tower 4 is between 2 and 10 minutes.
The product of the present invention is believed to be of the general formula (Z-O~r,Alr,~OE~ m(Cl)m, wherein m is greater than 0. However, it is dif f icult to provide an exact empirical f ormula because the product of the invention can exist in various forms. Three P 1PS: of these forms are given below:
\
Al - OH Al - OH Al - Cl 20 Z - O Z - O Z - o \
Al - OH Al - OH Al - Cl /
Z - O Z - O Z -- O
Al - OH Al - Cl Al - OH
/
Z - O . Z - O Z - O
30 Al - Cl Al - OH
Modif ications to this general example are p~ ; hl P .
For example, the mixture of activated zeolite and aqueous pOlyAl 'n; ' l~ride can first be dried at less than 100C (to avoid ~1P_ __-;n~ the polyal, ;n; ' l~lride) and under vacuum if that is W~ ~'i12~2G6 PCTIAU~5/OUl22 deemed necessary to further reduce the likelihood of the polyaluminil hlnride tlf- _~~;n~, and then the mixture is heated between 250 and 600C.
The product of the invention is usually used at the 5 rate of 0.1 g to 10 g/l of waste water, more particularly, O . 2 to O . 5 g/1 of waste water .
SPECIFIC
Example 1 A mineral containing about 60 weight percent of clinoptilolite and having a grain size of not more than 250 micron is mixed in a weight ratio of 1: 1 with an af~ueous polyA~ ;n; ' lnride solution having a polyaluminiumchloride content of about 50 weight percent. To this mixture is added hydrochloric acid, until a p~l of less than 1. 5 is obtained. The mixture is fed to the top of the spray tower where it is atomized by the rotating disk. Air at a temperature of 150 to 200C is fed to the top of the spray tower. The rPc;cl~onre time 2 0 of the mixture in the tower is about 3 to 5 minutes. The solid composite product leaves the tower at a temperature of about 90 to 95C with a water content of about 2 to 5 weight percent.
Example 2 Waste water was used from an optical plant and contained a large amount of hydrorA rbon c, a high value of rhPm; rAl oxygen d~fir; Pnry and a signif icant quantity of heavy metal ions, such as zinc and nickel.
~ WO95124266 2 1 ~ 5 ~ 27 PCT/AU!?5/00122 The product of the invention was prepared in accordance with Example 1 aoove and the waste water was treated with the following ~ ~lds for cornparison:
A ) A1 z ( 5O4 ), Aluminiumsulf ate B) Zeolite + Alz(SO4)3 mixed 1: 1 C ) Zeolite + PAC mixed ( PAC = Poly;l 1 n; ~ 1 nride ) D) Product according to Example 1 All analyses were conducted according to the German standard DIN.
o ~c A-D were tested at 1 g/1 of waste water and the pH adjusted to 8 with Ca(OE~) z .
Af ter addition of the product, the waste water was stirred at 500 rpm at 18 to 20C for 10 minutes.
The resultant precipitate was separated by filtration using a paper filter. The filtration rate was measured.
The determination of the heavy metal ion content was perf ormed with an atomic absorption spe~, LL ~ ~L .
The results are shown in Table I.
21 ~5 1 27 O O ~ u~ ~ _I O O ~ ~I' O ~D ~1 0 0 0 0 ~n ~D r1 O ~ t V V V Irl a ~
o o O
O O Lr) ~D ~ ~ O, o ~D ~D O O O o .) ~ rt ~.) ~1 ~rl O O ~7 N a. ~O O O O
O N ~ m r o o ~ ~r ~D " O O
m c , J U7 - o o m o ~ N ~t ' O ' O N 1'7 N ~i 0 0 0 0 O O ~ U~ ~ O o O
rt = E N r~ ~ E ~ r = æ
SUBSTITUTE SHEET (RULE 26) Wo 9s~24266 2 1 ~ 5 ~ 2 7 rCT/~U9~/00122 Example 3 Waste water from a bath for degreasing and - phosphating metal was used. Products A-D were tested at 5 g/ 1 of waste water .
In all other respects, the same conditions and mea:.uL~ ~s were undertaken as in Example 2.
The results are shown in Table II.
The product of the invention is multi-functional.
Due to the presence of anionic oxygen, it can act as an ion ~ h~n~ r to absorb, for example, heavy metal cations; as it is partly protonated, it can exchange those protons to appropriately proton-acceptable groups such as those f ound in dyes; the ~ mini ~ lnride groups can split off chloride anions thus exhibiting cationic properties to enable the removal of, f or example, phosphate anions.
Importantly, by varying the degree of activation of the ~ rni nnci l i ~atF~ L and the ratio of polyaluminiumchloride, these multi-functional properties can be adjusted to suit the waste material being heated.
By using the present invention, clarification of waste water and other })nl 1 I~t~d materials can be achieved more effectively than prior pLocesses and of f ers at least the f nl 1 owi n~ advantages:
- it is pH neutral;
wo9~cl24266 2~ 851 27 Pcr~Auss/00122 ~
- it is not toxic;
- it is suitable for use in flotation and R~ ation tanks;
- it des~Ahl;7~R sl~C~nc;ons~ dispersions and 5 emulsions;
- the only anion present is hydroxyl;
- it can be used over a wide pH range;
- it is amphoteric and particularly suited for the elimination of heavy metal cations and phosphate anions;
- it reduces chemical oxygen deficiency, biological oxygen def iciency and adsorbable organic h~ on~ted hydrocarbons;
- it decreases the amount of sludge while simult~n~ouRly increasing dry matter content;
- it does not swell;
- it is ec~nl i r;ll; and - is not harmful to the environment.
Claims (20)
1. A method for the preparation of a compound of the general formula:
(ZO)nAln(OH)n-mClm or a compound of closely related empirical formula, wherein Z is derived from an aluminosilicate material, said method comprising:
1) activating said material; and 2) heating the thus activated material in the presence of an alumino compound.
(ZO)nAln(OH)n-mClm or a compound of closely related empirical formula, wherein Z is derived from an aluminosilicate material, said method comprising:
1) activating said material; and 2) heating the thus activated material in the presence of an alumino compound.
2. A method as defined in Claim 1, wherein the material is a zeolite-containing mineral.
3. A method as defined in Claim 2, wherein the zeolite content of the mineral is 40 to 95% by weight.
4. A method as defined in Claim 2 or Claim 3, wherein the Si:Al ratio of the zeolite is greater than 3.
5. A method as defined in Claim 4, wherein the zeolite is of a clinoptilolite structure.
6. A method as defined in any one of Claims 2 to 5, wherein the mineral is finely divided to a particle size of 250 microns or less.
7. A method as defined in any one of Claims 2 to 6, wherein the mineral is activated by treating with acid or by subjecting the mineral to ammonium ion exchange.
8. A method as defined in Claim 7, wherein the mineral is activated by treatment with hydrochloric acid.
9. A method as defined in any one of Claims 1 to 8, wherein the alumino compound is a polyaluminium salt.
10. A method as defined in Claim 9, wherein the polyaluminium salt is polyaluminiumchloride.
11. A method as defined in any one of Claims 1 to 10, wherein the alumino compound is added as an aqueous solution.
12. A method as defined in any one of Claims 2 to 11, wherein the ratio of mineral:alumino compound is in the range of 1:0.01 to 1:2 by weight.
13. A method as defined in Claim 12, wherein the ratio is 1:1.
14. A method as defined in any one of Claims 2 to 13, wherein the activated mineral and the alumino compound are heated together at a temperature which is in the range 100 to 600°C.
15. A method as defined in Claim 14, wherein the temperature is 300°C.
16. A method as defined in Claim 11 wherein the activated mineral and aqueous alumino compound are heated at a temperature in the range of 150 to 250°C with the simultaneous evaporation of water.
17. A method as defined in any one of Claims 1 to 15 wherein the activated material and alumino compound are first dried at a temperature less than 100°C
and then heated to a temperature between 250 and 600°C.
and then heated to a temperature between 250 and 600°C.
18. An agent for the treatment of waste water and other polluted materials, said agent comprising a compound of the general formula:
(ZO)nAln(OH)n-mClm or a compound of closely related empirical formula, wherein Z is derived from an aluminosilicate material.
(ZO)nAln(OH)n-mClm or a compound of closely related empirical formula, wherein Z is derived from an aluminosilicate material.
19. An agent as defined in Claim 18, when prepared by a method as defined in any one of Claims 1 to 17.
20. A method of treating waste water and other polluted materials by the application of an agent as defined in Claim 18 or Claim 19.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4408302.5 | 1994-03-11 | ||
| DE4408302A DE4408302C2 (en) | 1994-03-11 | 1994-03-11 | Process for the manufacture and use of a solid composite product for water treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2185127A1 true CA2185127A1 (en) | 1995-09-14 |
Family
ID=6512547
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002185127A Abandoned CA2185127A1 (en) | 1994-03-11 | 1995-03-10 | Waste treatment agent |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0671210B1 (en) |
| JP (1) | JPH10503459A (en) |
| AT (1) | ATE193463T1 (en) |
| AU (1) | AU704478B2 (en) |
| BG (1) | BG61968B1 (en) |
| BR (1) | BR9507410A (en) |
| CA (1) | CA2185127A1 (en) |
| DE (2) | DE4408302C2 (en) |
| FI (1) | FI963550A (en) |
| HU (1) | HUT77690A (en) |
| NO (1) | NO963797L (en) |
| WO (1) | WO1995024266A1 (en) |
| ZA (1) | ZA952006B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19515932C2 (en) * | 1995-05-02 | 2000-09-21 | Feistel Gmbh Industrievertretu | Use of a zeolite composite product |
| DE19923644B4 (en) * | 1999-05-22 | 2008-09-04 | Hartsteinwerke Vogtland Gmbh & Co. Kg | Process for the separation of pollutants from water |
| KR100960151B1 (en) * | 2009-09-10 | 2010-05-28 | 주식회사 삼우 | Coagulant composition and manufacturing method thereof |
| CZ308211B6 (en) * | 2011-11-08 | 2020-03-04 | Vysoká Škola Báňská Technická - Univerzita Ostrava | Method of removing phosphates from household waste water |
| CN104062335B (en) * | 2013-03-18 | 2016-08-03 | 四川碧朗科技有限公司 | The method and apparatus that electrochemistry COD associating water quality heavy metal ion is monitored automatically |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2602416A1 (en) * | 1976-01-23 | 1977-07-28 | Basf Ag | Zeolite mouldings contg. basic aluminium chloride binders - produced with flowable zeolite powders contg. water and with amorphous binder |
| DE2926606A1 (en) * | 1979-07-02 | 1981-01-22 | Henkel Kgaa | Waste water purification by pptn. - using alkali-and or alkaline earth aluminosilicate in addn. to standard precipitant and flocculant |
| US4247524A (en) * | 1979-10-01 | 1981-01-27 | Atlantic Richfield Company | Preparation of zeolite A by hydrothermal treatment of clinoptilolite |
| FR2472951A1 (en) * | 1980-01-07 | 1981-07-10 | Degremont | Three stage reaction appts. for continuous prepn. of coagulant(s) - esp. activated silica or alumino:silicate gel or basic aluminium chloride |
| JPS57187008A (en) * | 1981-05-14 | 1982-11-17 | Nippon Solid Co Ltd | Molding of flocculating agent |
| JPS57201506A (en) * | 1981-06-03 | 1982-12-10 | Minato Sangyo Kk | Purifying agent of water |
| SU1214594A1 (en) * | 1983-11-24 | 1986-02-28 | Всесоюзный научно-исследовательский и проектный институт галургии | Method of removing surface-active substances from brines |
| US4542118A (en) * | 1984-02-02 | 1985-09-17 | W. R. Grace & Co. | Catalyst manufacture |
| JPS60209214A (en) * | 1984-04-03 | 1985-10-21 | Fujio Hotta | High-speed clarification process of filthy water |
| JPS61133140A (en) * | 1984-11-30 | 1986-06-20 | Nippon Soda Co Ltd | Composition for purifying water |
| US5070053A (en) * | 1987-10-30 | 1991-12-03 | Exxon Research And Engineering Company | FCC catalyst composition and method of making same |
| FR2632944B1 (en) * | 1988-06-17 | 1990-10-12 | Ceca Sa | PROCESS FOR THE PREPARATION OF ZEOLITIC MOLECULAR SIE AGGLOMERES WITH ZEOLITIC BINDER |
| JPH0356104A (en) * | 1989-07-25 | 1991-03-11 | Fujio Hotta | High speed clarifier for polluted water |
| US5145816A (en) * | 1990-12-10 | 1992-09-08 | Mobil Oil Corporation | Method for functionalizing synthetic mesoporous crystalline material |
| US5096871A (en) * | 1990-07-03 | 1992-03-17 | Alcan International Limited | Alumina-alkali metal aluminum silicate agglomerate acid adsorbents |
| SE9103661D0 (en) * | 1991-12-12 | 1991-12-12 | Kemira Kemi Ab | PROCEDURES FOR PREPARING A COAGULATING CHEMICAL |
-
1994
- 1994-03-11 DE DE4408302A patent/DE4408302C2/en not_active Expired - Fee Related
-
1995
- 1995-03-10 AU AU19408/95A patent/AU704478B2/en not_active Ceased
- 1995-03-10 ZA ZA952006A patent/ZA952006B/en unknown
- 1995-03-10 AT AT95103514T patent/ATE193463T1/en not_active IP Right Cessation
- 1995-03-10 HU HU9602472A patent/HUT77690A/en unknown
- 1995-03-10 BR BR9507410A patent/BR9507410A/en not_active Application Discontinuation
- 1995-03-10 WO PCT/AU1995/000122 patent/WO1995024266A1/en active Application Filing
- 1995-03-10 CA CA002185127A patent/CA2185127A1/en not_active Abandoned
- 1995-03-10 EP EP95103514A patent/EP0671210B1/en not_active Expired - Lifetime
- 1995-03-10 DE DE59508404T patent/DE59508404D1/en not_active Expired - Fee Related
- 1995-03-10 JP JP7523119A patent/JPH10503459A/en active Pending
-
1996
- 1996-09-10 FI FI963550A patent/FI963550A/en unknown
- 1996-09-10 NO NO963797A patent/NO963797L/en unknown
- 1996-10-08 BG BG100890A patent/BG61968B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BG61968B1 (en) | 1998-11-30 |
| BG100890A (en) | 1997-09-30 |
| HUT77690A (en) | 1998-07-28 |
| BR9507410A (en) | 1997-09-09 |
| DE4408302C2 (en) | 1996-04-04 |
| ATE193463T1 (en) | 2000-06-15 |
| FI963550A (en) | 1996-09-17 |
| NO963797D0 (en) | 1996-09-10 |
| ZA952006B (en) | 1995-10-13 |
| EP0671210A2 (en) | 1995-09-13 |
| FI963550A0 (en) | 1996-09-10 |
| EP0671210B1 (en) | 2000-05-31 |
| DE4408302A1 (en) | 1995-10-12 |
| MX9604012A (en) | 1997-12-31 |
| HU9602472D0 (en) | 1996-11-28 |
| JPH10503459A (en) | 1998-03-31 |
| DE59508404D1 (en) | 2000-07-06 |
| NO963797L (en) | 1996-11-11 |
| AU704478B2 (en) | 1999-04-22 |
| EP0671210A3 (en) | 1995-11-22 |
| AU1940895A (en) | 1995-09-25 |
| WO1995024266A1 (en) | 1995-09-14 |
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