CA2193839A1 - Elimination of waste materials in paper production - Google Patents
Elimination of waste materials in paper productionInfo
- Publication number
- CA2193839A1 CA2193839A1 CA002193839A CA2193839A CA2193839A1 CA 2193839 A1 CA2193839 A1 CA 2193839A1 CA 002193839 A CA002193839 A CA 002193839A CA 2193839 A CA2193839 A CA 2193839A CA 2193839 A1 CA2193839 A1 CA 2193839A1
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- CA
- Canada
- Prior art keywords
- agent
- paper
- polymer
- compound
- mineral
- 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
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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
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention is directed to an agent to remove contaminants from water used in the production of paper and related products, of the general formula: (ZO)nAln(OH)n-mClm (or of closely related empirical formula), which, optionally, has been further coated with a polymer, wherein Z is derived from an aluminosilicate material. The agent 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 a cationic agent, followed by coating with a polymer. The preferred aluminosilicate is a zeolite-containing mineral of a clinoptilolite structure and the preferred cationic agent is selected from polyaluminiumchloride, epichlorohydrin (or a polymer derivative thereof) or dicyanodiamide. The preferred coating polymer is polyacrylamide. Use of the agent leads to production increase, reduction of sludge generation, reduction of contaminant load, reduction in chemical oxygen demand and a cost saving.
Description
~ ~0~34684 21 93~39 PCTIAU96100261 TITLE: ELIMINATION OF WASI'E MATERIALS IN PAPER PRODUCTION
FIELD OF THE INVENTION
THIS INVENTION relates to the elimination of waste materials and other pollutants from water. In particular, it is directed to the production and use of compounds which efficiently clarify or otherwise remove these waste materials and other pollutants during the manufacture of paper, cardboard and similar products.
BACRGROUND OF THE I~VENTION
Up until approximately the early 1970's, cellulose and wood pulp were used almost exclusively for the manufacture of paper and related pLGdu~L~. These were clean, primary raw materials without significant contaminants. Increasingly however, "new" paper has been manufactured by ' fn~ng these raw materials with "recycled" paper, that is, paper which has been previously manufactured, used and then returned to the manufacturing industry to be used again in the preparatlon of fresh paper.
With the use of this recycled paper, comes the introduction of signi~icant contaminants into the paper manufacturing process. Typicsl contaminants are resins, starch, binders, adhesives/gums/glues and other compounds - usually synthetic - introduced in the manufacturing process to provide specific qualities or properties to the original paper such as brightness and strength.
Further, it ls a requirement of most GOY~ L Authorities today that polluted water and other waste material generated by industry are adequately treated be~ore their disposal. It is of particular concern to ensure that these industrial by-products are disposed of carefully without W096/34~4 7 l ~ , 3 ~ PCTIAU~0261 ~
undue harm to the environ~ent. This has lead to the development o~ "closed" systems whereby the water th~t is required in the manufacture of paper and related products is cont~r~ qly circulated within the manufacturing plant until lt is essentially 211 Gnn! a resulting in only minimal disahsrge of "waste" water to the outside environment. In fact, it is not 1r ~ to manufacture "new" paper ~rom l00~ recycled paper in a totally closed system.
However, such processes face a number of problems, ;n~~ ing (a) s~ LaLiCn within the system leading to the shutting down of the process while cleansing is undertaken; and (b) as the "pollutants" and the agents to remove them are in~uL~oL~Led as a , ?nt of the final pape~ product, they czn have an adverse effect on the final paper quality, particularly with respect to moisture content, unwanted staining and lower than desired ~ Lh - these latter problems are further amplified by the in~l1cinn of ~ ry agents to bring the final paper guality back to the desired level but which, ln turn, effectively add to the quantity of "contaminants" present in the manufacturing process.
One such quality is the sizing of paper, that is, the degree to which the paper will repel water. Slzing is expressed as how much water paper or cardboard can absorb per minute over a specific area and is known as the COBB
value.
The principle of sizing is that anionic adhesive agents added to the paper pulp are flocculated and then undergo ion exchange by the addition of suitable cationio additives. They are then abls to be absorbed onto the paper fibre.
~ W096/34684 ~ 3 ~' 3 ~
However, anionic contaminants lead to fluctuations o~ the COB3 value in the fibre product and if too much sizing agent is added, strong foa;ning occurs, leading to problems in the production of the final paper product.
The presence of contaminants causes other problems, for example, variations in weight and moisture content of the final paper product and adverse effects on the rh~mir~l oxygen demand, the biological oxygen demand and the quantity of halogenated hydrocarbons.
With a relatively high biological oxygen demand, a satisfactory procedure for removing the thus present bacteria and other microorganisms from the circulating water andJor their incorporation into the final paper product has not yet been satisfactorily resolved.
It is a complex task to handle and utilise these contaminants because they have quite different pL~peL~ies, particulate sizes and reactivities; they may appear in solution, in colloid form, as a suspension or dispersion;
in small or large particulate size.
Conventional ~L~dU~ that have been used in an attempt to alleviate the afore-mentioned problems include microtalcum, cationised microtalcum, altonite/bentonite, cationic polymers and polyaluminiumchloride.
Microtalcum, due to its large surface area, has the ability to absorb small, sticky particles. ~owever, a great disadvantage is that relatively large quantities of microtalcum (up to 1.5~) must be employed which is detrimental to the strength of the final paper and it does not remove colloidal or anionic contaminants.
wog~ ~ 2 ~ ~ 3 c~ ~ q PCT/AUg~/OO~I ~
In an attempt to increase the usefulness of microtalcum by giving it the property of being able to remove anionlc contaminants, cat;on1q~ microtalcum wes developed. As microtalcum is essentially ~h~m;c~lly inert, this could only be achieved by coating the microtalcum with a cationic substance, for example, polydadmac. ~owever, this coating was readily washed off by the water of the paper making process and thus it only removed mlnLmal anionic contaminants before reverting to microtalcum with its attendant disadvantages referred to above.
Altonite and bentonite are insert silicate minerals and function similarly to mLcrotalcum. }lowever, they display no significant higher absorption capacity for contaminants then that by microtalcum and are more expensive to purchase.
Strongly ca~;oniq~d polymers, developed in the mid 1980's-mid l990's, have been partlally successful in that they remove anionic contaminants. However, the resultant composites have proved virtually ;mrn~1hle to remove from the system effectively. They are also expensive to manufaoture and require high application rates and have thus provided lln~ ~ ;c~l.
Poly~1nm;n;~ 'lmride (PAC~ has been used successfully in the treatment of e~luent and similar waste water and is a f~vuu~d coagul2nt in 5~; La~lon tanks.
Much research has been undertaken to improve to efficiency of this agent. For example, in a method described in Japanege Un~m;n~d Patent Publication No. 60-209214 (Application No. 59-65078, filed April 3, 1984) it is blended with ~inely divided all~m;n~c~licate-containing minerals to provide a means for improving the time taken for sedimentation to be effeoted. In Japanese Un~Y~min~
~ W096~4684 2 ~ 9 3 ~3 3 ~ PCTiAU96100261 Patent Publication No. 3-05610~ (Application No. 1-192232, filed July 25, 1989), separate quantities of an aluminosilicate mineral, particularly one containing a zeolite, are individually treated with (1) sulfuric acid to give a product "a", (2) with hydrochloric aoid followed by polyaluminiumchloride 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 polluted water.
While these improved processes may be successful, and PAC
offers many properties which appear suited to the removal of contaminants from water, PAC has a major disadvantage lf it is to be used in the paper industry, namely, its acidity (pH range approximately 1 to 3). As it is acidic, PAC
cannot be used wherein a contaminant is a carbonate, for example, calcium carbonate, as it reacts with carbonates at a pH of <6.3 to produce a ~as which is detrimental in the PLOdU~LiOn of paper leading to significant contamination of the final product.
There thus remains a need for an econ: ~r~l material which can remove contaminants during the manufacture of paper or related pLuduu~s (in a closed system, if n~cPsq~ry), and which can be incuL~uLated into the final product without detrimental effect on the required properties of that product.
It is thus an object of the present invention to eliminate, or at least ameliorate, one or more of the above problems and to provide an agent for use in the removal of cu..i 'n~nts from water used in the production of paper and related products which is ~nn, ~al to produce, effective in the removal of more than one type of contaminant and which can be incorporated into the final product without t.j ~ ; ( ' ~ :~
W09613~W ~ J ~ PCT/~U9~00261 detrimental effect on the required properties of that product.
SUM~ARY OF TH~ INVENTION
It has now been estRhl f Ch~ that compounds similar to those described in International Patent Application No.
PCT/AU95/00122, the entire content of which i5 incu~oL~ted herein by IefeLer~, with or without further modification, can be used to meet this ob~fectlve.
Therefore, according to a first aspect of the present invention, there is provided an agent for use in the removal of contaminants from water used in the production of paper and related products, said agent comprising a _ In~ of the general formula:
(zo)nAln(OH)n-mclm or a compound of closely related empirical formula, which, optionally, has been further coated with a polymer, wherein Z is derived from an all~mfn~sflfr-Rte material.
As a second aspect of the present invention there is provided a method for the preparation of a oompound of the general formula:
( Z~ )nAln( OE~ )n-mClm or a compound of closely related emp$rical formula, wherein Z is derived from an alnmfnrsflirRte material, said method comprising:
l~ activating said material ~ wog61346x4 ~ 3,~3 ~ pCT/~U96/00261 2) heating the thus activated material in the presence of a cationic agent; and 3) optionally, coating the resultant product with a polymer.
A third aspect of the present invention is a method of removing contaminants from water used in the production of paper and related products, said method oomprising treating the water with a _ ,a~ln~ having the following general formula:
(zo)nAln(oH)n-mclm or a~ , In~ of closely related empirical formula, which, optionally, has been further coated with a polymer, wherein Z is derived from an ~lum~n~c~licate material.
As a fourth aspect of the present invention, there is prcvided a method of marufacturing paper and related products, wherein contaminants from water used in the production of the paper and related products have been removed by a compound as hereinbefore described and in~ol~v ~ted into the iinal paper or related product.
The aluminosilicate can be a natural or synthetic material.
Preferably, the material is a zeolite-containing mineral.
Preferably, the zeolite content of the mineral is at least 40~ by weight.
.
Preferably, the Si:Al ratio of the zeolite is greater than 3.
W096l3~84 ;2 1 3 .$ ~ ~ 9 PCT/A~6/002GI
More preferably, the quartz content of the zeolite ls not more than 5~ by welght, preferably not more thzn 1~.
Most preferably, the zeolite is of a clinoptilolite structure.
Most prefera~ly, the mineral is finely divided to a particle size ranging between 0.1 and 30 ,um.
Preferably the zeolite-containing mineral is activated by treating with acid or by sub~ecting said mineral to ;llm ion ~Y~.~Rnge ~
More preferably, the zeolite-containing mineral is activated by treatment with hydrochloric acid.
L
Preferably, the cationic agent is selected from an alumino compound, epiohlorohydrin or a derivative thereof, or dicy~nn~;Rm;~, Preferably, the alumino ( --u-ld is a polyaluminium salt.
More preferably, the polyaluminium salt is polyaluminiumchloride.
Preferably, the ratio of mineral : alumino compound i5 in the range of 1:0.1 to 1:5 by weight.
More preferably, the ratio of mineral : alumino ~ ~ is in the range of I:l to 1:2 by weight.
Most preferably, the ratio is 1:1 by weight.
Preferably, the activated mineral and the alumino ~ , ,u~ld are heated together at a temperature which is in the range 100 - 600~C.
-~ W096~4684 21 9 3 ~ ~9 pcTlAU96l0o26l More preferably, the heating is undertaken at about 300~C.
Preferably, the epichlorohydrin derivatives are polymers of ~pirhl~rohydrin which, optionally, have been further mixed with an acid, preferably, --1 Am~ n~ acid.
Preferably the coating polymer is an amide.
More preferably, the amide is a polyamide.
Most preferably, the polyamide is polyacrylamide.
Preferably, the product of the invention is granulated to a particle size of 0.25 - 100 um.
Mixt~res of agents ~L~paLed by the present invention can also be used, i.e., mixtures selected from a first agent in~uL~L~ting polyaluminiumchloride as the cationic agent;
a second agent incorporating dicy~no~ia~d~ as the cationic agent; a third agent inCor]?orating ~r~ rhl orohydrin as the catio~ic agent; and a fourth agent incorporating polyaluminiumchloride as the caticnic agent and then subsequently coated with a cationic polymer.
~ESCRIPTION OF THE INVENTION
GENE~AL EXAMPLE
A naturally occurring, acid-resistant, thermostable, zeolite-containing mineral is first finely divided by any convenient means and then activated by washing with hydrochlcric acid. An aqueous polyaluminiumchloride 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.
W096~468~ 2 1 , 3 ~ ~ ~ PCTIAU~00261 The product formed preferably has a water content of less than 10 percent by welght, more prei'erably less thsn 5 percent by weight.
More details on the preparation of such composites can be found in the aforementioned International Patent Application No. PCT/AU95/00122.
The thus - prepared composites are then coated with the required polymer by any conventional means known in the art. For example, by dipping in, or spraying on, a solution of the polymer and then drying to produce the coated compos~te.
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 the partially hydrolized cationic agent, ior example, polyaluminium chloride.
In more detail, activating by washing with hydrochloric acid forms a protonated zeolite and a metal salt. For example:
(ZO)nAl(ONa) + HCl ~ ~ZO)nAlOH + NaCl ~ Upon treatment with polyslv~n~l loride, a composite i8 formed in a number of ways. For example:
(1~ (ZO)nAlOH + Aln(OH)mC13n_m ' ~ZO)nAlOAln(OH)m_lC13n_m + H20 (2) (ZO~IlAlOH + Aln(OH)mC13n_m ~ (ZO)nAlOAl~OH)mC13n (m+1) + HCl ~ W09G~4684 2 ' , 3 3 3 1 PCT/AUg6/00261 The product of the present invention is thus believed to be approximately of the general formula ~ZO)nAln(OH)n_m(Cl)m, wherein m is greater than 0. However, it is difficult to provide an exact empirical formula because the product of the invention can exist in various ~orms. Three ~ q of these forms are given below:
Z - O Z - O O - Z
\
A1 - OH Al - OH A1 - C1 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
Al - Cl Al - OH
SPECIFIC EXAMPLES
The pLucedu-~ described above in the General Example was undertaken with a number of zeolite-containing minerals from various sources, particularly from China, Hungary and Bulgaria, to produce a number of composites hereinafter designated as ZEOPAC VP1, ZEOPAC 1, ZEOPAC 2, ZEOPAC 3 and Z~OPAC 4.
W096~4~4 ~ 9 PCT~AUgC/00~6l WET ST~ENGTH
Tests were carried out to determine the wet xLLenyu~ of paper prepared from bleached spruce/pine wood pulp which had been deliberately contaminated by the addltional of ground wood pulp filtrate (an anLonic contaminant) at ~u--uenLL~Lions of 0, 2 and 4 ,u mol~g of fibre. ZEûPAC VPl was selected as the composlte of the inv&ntion and was used at 0, 1 and 2 percent concentration. The wet ~LLenyLI-agent was MARVESIN T35AS - a polyamide-amine-epichlorohydrin resin - at concentrations of 2, 4 and 6 percent. The test mztrix were thus as follows in Table 1.1.
The resultant wet strength peLuu-.L~ges are presented in Table 1.2.
These results are also illustrated graphically in Figures 1.1, 1.2 and 1.3.
The wet strength increa5ed almost linearly wlth the increase in quantlty of the wet ~LLenyLll agent, and the anlonic contaminants, not surprisingly, ~1m~n~h the ef~ect of the wet ~LenyLll agent. However, by the additlon of ZEûPAC VP1, this reduction in wet ~LLUI1YL1I can be curbed, and the composite of the invention is thus , , cating for the disadvantageous effect of the contaminant present.
DRY CûNTENT, pH and CATIONIC CHARGE
The dry content was determined after drying composites of the invention for three hours at 80~C at 1 atmosphere. The pH was measured immediately after production of a g~ ZEûPAC
aqueous sllcp~nci~n and 30 minutes thereafter.
WOgCt34~4 ~ 83q PCTtAU9C~261 T h e c ati o n i c c h a r g e was d e te r m i n e d b y polyelectrolytetitratlon (~'ET).
The appropriate parameters are given in Table 2.l.
The cationic surface charge in ac~n~n3 order is ZEOPAC 4, ZEOPAC l, ZEOPAC 2, ZEOPAC 3.
Sieve filtrates from paper production were analyzed for dissolved electrolytes with and without ZEOPAC l to ZEOPAC
FIELD OF THE INVENTION
THIS INVENTION relates to the elimination of waste materials and other pollutants from water. In particular, it is directed to the production and use of compounds which efficiently clarify or otherwise remove these waste materials and other pollutants during the manufacture of paper, cardboard and similar products.
BACRGROUND OF THE I~VENTION
Up until approximately the early 1970's, cellulose and wood pulp were used almost exclusively for the manufacture of paper and related pLGdu~L~. These were clean, primary raw materials without significant contaminants. Increasingly however, "new" paper has been manufactured by ' fn~ng these raw materials with "recycled" paper, that is, paper which has been previously manufactured, used and then returned to the manufacturing industry to be used again in the preparatlon of fresh paper.
With the use of this recycled paper, comes the introduction of signi~icant contaminants into the paper manufacturing process. Typicsl contaminants are resins, starch, binders, adhesives/gums/glues and other compounds - usually synthetic - introduced in the manufacturing process to provide specific qualities or properties to the original paper such as brightness and strength.
Further, it ls a requirement of most GOY~ L Authorities today that polluted water and other waste material generated by industry are adequately treated be~ore their disposal. It is of particular concern to ensure that these industrial by-products are disposed of carefully without W096/34~4 7 l ~ , 3 ~ PCTIAU~0261 ~
undue harm to the environ~ent. This has lead to the development o~ "closed" systems whereby the water th~t is required in the manufacture of paper and related products is cont~r~ qly circulated within the manufacturing plant until lt is essentially 211 Gnn! a resulting in only minimal disahsrge of "waste" water to the outside environment. In fact, it is not 1r ~ to manufacture "new" paper ~rom l00~ recycled paper in a totally closed system.
However, such processes face a number of problems, ;n~~ ing (a) s~ LaLiCn within the system leading to the shutting down of the process while cleansing is undertaken; and (b) as the "pollutants" and the agents to remove them are in~uL~oL~Led as a , ?nt of the final pape~ product, they czn have an adverse effect on the final paper quality, particularly with respect to moisture content, unwanted staining and lower than desired ~ Lh - these latter problems are further amplified by the in~l1cinn of ~ ry agents to bring the final paper guality back to the desired level but which, ln turn, effectively add to the quantity of "contaminants" present in the manufacturing process.
One such quality is the sizing of paper, that is, the degree to which the paper will repel water. Slzing is expressed as how much water paper or cardboard can absorb per minute over a specific area and is known as the COBB
value.
The principle of sizing is that anionic adhesive agents added to the paper pulp are flocculated and then undergo ion exchange by the addition of suitable cationio additives. They are then abls to be absorbed onto the paper fibre.
~ W096/34684 ~ 3 ~' 3 ~
However, anionic contaminants lead to fluctuations o~ the COB3 value in the fibre product and if too much sizing agent is added, strong foa;ning occurs, leading to problems in the production of the final paper product.
The presence of contaminants causes other problems, for example, variations in weight and moisture content of the final paper product and adverse effects on the rh~mir~l oxygen demand, the biological oxygen demand and the quantity of halogenated hydrocarbons.
With a relatively high biological oxygen demand, a satisfactory procedure for removing the thus present bacteria and other microorganisms from the circulating water andJor their incorporation into the final paper product has not yet been satisfactorily resolved.
It is a complex task to handle and utilise these contaminants because they have quite different pL~peL~ies, particulate sizes and reactivities; they may appear in solution, in colloid form, as a suspension or dispersion;
in small or large particulate size.
Conventional ~L~dU~ that have been used in an attempt to alleviate the afore-mentioned problems include microtalcum, cationised microtalcum, altonite/bentonite, cationic polymers and polyaluminiumchloride.
Microtalcum, due to its large surface area, has the ability to absorb small, sticky particles. ~owever, a great disadvantage is that relatively large quantities of microtalcum (up to 1.5~) must be employed which is detrimental to the strength of the final paper and it does not remove colloidal or anionic contaminants.
wog~ ~ 2 ~ ~ 3 c~ ~ q PCT/AUg~/OO~I ~
In an attempt to increase the usefulness of microtalcum by giving it the property of being able to remove anionlc contaminants, cat;on1q~ microtalcum wes developed. As microtalcum is essentially ~h~m;c~lly inert, this could only be achieved by coating the microtalcum with a cationic substance, for example, polydadmac. ~owever, this coating was readily washed off by the water of the paper making process and thus it only removed mlnLmal anionic contaminants before reverting to microtalcum with its attendant disadvantages referred to above.
Altonite and bentonite are insert silicate minerals and function similarly to mLcrotalcum. }lowever, they display no significant higher absorption capacity for contaminants then that by microtalcum and are more expensive to purchase.
Strongly ca~;oniq~d polymers, developed in the mid 1980's-mid l990's, have been partlally successful in that they remove anionic contaminants. However, the resultant composites have proved virtually ;mrn~1hle to remove from the system effectively. They are also expensive to manufaoture and require high application rates and have thus provided lln~ ~ ;c~l.
Poly~1nm;n;~ 'lmride (PAC~ has been used successfully in the treatment of e~luent and similar waste water and is a f~vuu~d coagul2nt in 5~; La~lon tanks.
Much research has been undertaken to improve to efficiency of this agent. For example, in a method described in Japanege Un~m;n~d Patent Publication No. 60-209214 (Application No. 59-65078, filed April 3, 1984) it is blended with ~inely divided all~m;n~c~licate-containing minerals to provide a means for improving the time taken for sedimentation to be effeoted. In Japanese Un~Y~min~
~ W096~4684 2 ~ 9 3 ~3 3 ~ PCTiAU96100261 Patent Publication No. 3-05610~ (Application No. 1-192232, filed July 25, 1989), separate quantities of an aluminosilicate mineral, particularly one containing a zeolite, are individually treated with (1) sulfuric acid to give a product "a", (2) with hydrochloric aoid followed by polyaluminiumchloride 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 polluted water.
While these improved processes may be successful, and PAC
offers many properties which appear suited to the removal of contaminants from water, PAC has a major disadvantage lf it is to be used in the paper industry, namely, its acidity (pH range approximately 1 to 3). As it is acidic, PAC
cannot be used wherein a contaminant is a carbonate, for example, calcium carbonate, as it reacts with carbonates at a pH of <6.3 to produce a ~as which is detrimental in the PLOdU~LiOn of paper leading to significant contamination of the final product.
There thus remains a need for an econ: ~r~l material which can remove contaminants during the manufacture of paper or related pLuduu~s (in a closed system, if n~cPsq~ry), and which can be incuL~uLated into the final product without detrimental effect on the required properties of that product.
It is thus an object of the present invention to eliminate, or at least ameliorate, one or more of the above problems and to provide an agent for use in the removal of cu..i 'n~nts from water used in the production of paper and related products which is ~nn, ~al to produce, effective in the removal of more than one type of contaminant and which can be incorporated into the final product without t.j ~ ; ( ' ~ :~
W09613~W ~ J ~ PCT/~U9~00261 detrimental effect on the required properties of that product.
SUM~ARY OF TH~ INVENTION
It has now been estRhl f Ch~ that compounds similar to those described in International Patent Application No.
PCT/AU95/00122, the entire content of which i5 incu~oL~ted herein by IefeLer~, with or without further modification, can be used to meet this ob~fectlve.
Therefore, according to a first aspect of the present invention, there is provided an agent for use in the removal of contaminants from water used in the production of paper and related products, said agent comprising a _ In~ of the general formula:
(zo)nAln(OH)n-mclm or a compound of closely related empirical formula, which, optionally, has been further coated with a polymer, wherein Z is derived from an all~mfn~sflfr-Rte material.
As a second aspect of the present invention there is provided a method for the preparation of a oompound of the general formula:
( Z~ )nAln( OE~ )n-mClm or a compound of closely related emp$rical formula, wherein Z is derived from an alnmfnrsflirRte material, said method comprising:
l~ activating said material ~ wog61346x4 ~ 3,~3 ~ pCT/~U96/00261 2) heating the thus activated material in the presence of a cationic agent; and 3) optionally, coating the resultant product with a polymer.
A third aspect of the present invention is a method of removing contaminants from water used in the production of paper and related products, said method oomprising treating the water with a _ ,a~ln~ having the following general formula:
(zo)nAln(oH)n-mclm or a~ , In~ of closely related empirical formula, which, optionally, has been further coated with a polymer, wherein Z is derived from an ~lum~n~c~licate material.
As a fourth aspect of the present invention, there is prcvided a method of marufacturing paper and related products, wherein contaminants from water used in the production of the paper and related products have been removed by a compound as hereinbefore described and in~ol~v ~ted into the iinal paper or related product.
The aluminosilicate can be a natural or synthetic material.
Preferably, the material is a zeolite-containing mineral.
Preferably, the zeolite content of the mineral is at least 40~ by weight.
.
Preferably, the Si:Al ratio of the zeolite is greater than 3.
W096l3~84 ;2 1 3 .$ ~ ~ 9 PCT/A~6/002GI
More preferably, the quartz content of the zeolite ls not more than 5~ by welght, preferably not more thzn 1~.
Most preferably, the zeolite is of a clinoptilolite structure.
Most prefera~ly, the mineral is finely divided to a particle size ranging between 0.1 and 30 ,um.
Preferably the zeolite-containing mineral is activated by treating with acid or by sub~ecting said mineral to ;llm ion ~Y~.~Rnge ~
More preferably, the zeolite-containing mineral is activated by treatment with hydrochloric acid.
L
Preferably, the cationic agent is selected from an alumino compound, epiohlorohydrin or a derivative thereof, or dicy~nn~;Rm;~, Preferably, the alumino ( --u-ld is a polyaluminium salt.
More preferably, the polyaluminium salt is polyaluminiumchloride.
Preferably, the ratio of mineral : alumino compound i5 in the range of 1:0.1 to 1:5 by weight.
More preferably, the ratio of mineral : alumino ~ ~ is in the range of I:l to 1:2 by weight.
Most preferably, the ratio is 1:1 by weight.
Preferably, the activated mineral and the alumino ~ , ,u~ld are heated together at a temperature which is in the range 100 - 600~C.
-~ W096~4684 21 9 3 ~ ~9 pcTlAU96l0o26l More preferably, the heating is undertaken at about 300~C.
Preferably, the epichlorohydrin derivatives are polymers of ~pirhl~rohydrin which, optionally, have been further mixed with an acid, preferably, --1 Am~ n~ acid.
Preferably the coating polymer is an amide.
More preferably, the amide is a polyamide.
Most preferably, the polyamide is polyacrylamide.
Preferably, the product of the invention is granulated to a particle size of 0.25 - 100 um.
Mixt~res of agents ~L~paLed by the present invention can also be used, i.e., mixtures selected from a first agent in~uL~L~ting polyaluminiumchloride as the cationic agent;
a second agent incorporating dicy~no~ia~d~ as the cationic agent; a third agent inCor]?orating ~r~ rhl orohydrin as the catio~ic agent; and a fourth agent incorporating polyaluminiumchloride as the caticnic agent and then subsequently coated with a cationic polymer.
~ESCRIPTION OF THE INVENTION
GENE~AL EXAMPLE
A naturally occurring, acid-resistant, thermostable, zeolite-containing mineral is first finely divided by any convenient means and then activated by washing with hydrochlcric acid. An aqueous polyaluminiumchloride 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.
W096~468~ 2 1 , 3 ~ ~ ~ PCTIAU~00261 The product formed preferably has a water content of less than 10 percent by welght, more prei'erably less thsn 5 percent by weight.
More details on the preparation of such composites can be found in the aforementioned International Patent Application No. PCT/AU95/00122.
The thus - prepared composites are then coated with the required polymer by any conventional means known in the art. For example, by dipping in, or spraying on, a solution of the polymer and then drying to produce the coated compos~te.
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 the partially hydrolized cationic agent, ior example, polyaluminium chloride.
In more detail, activating by washing with hydrochloric acid forms a protonated zeolite and a metal salt. For example:
(ZO)nAl(ONa) + HCl ~ ~ZO)nAlOH + NaCl ~ Upon treatment with polyslv~n~l loride, a composite i8 formed in a number of ways. For example:
(1~ (ZO)nAlOH + Aln(OH)mC13n_m ' ~ZO)nAlOAln(OH)m_lC13n_m + H20 (2) (ZO~IlAlOH + Aln(OH)mC13n_m ~ (ZO)nAlOAl~OH)mC13n (m+1) + HCl ~ W09G~4684 2 ' , 3 3 3 1 PCT/AUg6/00261 The product of the present invention is thus believed to be approximately of the general formula ~ZO)nAln(OH)n_m(Cl)m, wherein m is greater than 0. However, it is difficult to provide an exact empirical formula because the product of the invention can exist in various ~orms. Three ~ q of these forms are given below:
Z - O Z - O O - Z
\
A1 - OH Al - OH A1 - C1 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
Al - Cl Al - OH
SPECIFIC EXAMPLES
The pLucedu-~ described above in the General Example was undertaken with a number of zeolite-containing minerals from various sources, particularly from China, Hungary and Bulgaria, to produce a number of composites hereinafter designated as ZEOPAC VP1, ZEOPAC 1, ZEOPAC 2, ZEOPAC 3 and Z~OPAC 4.
W096~4~4 ~ 9 PCT~AUgC/00~6l WET ST~ENGTH
Tests were carried out to determine the wet xLLenyu~ of paper prepared from bleached spruce/pine wood pulp which had been deliberately contaminated by the addltional of ground wood pulp filtrate (an anLonic contaminant) at ~u--uenLL~Lions of 0, 2 and 4 ,u mol~g of fibre. ZEûPAC VPl was selected as the composlte of the inv&ntion and was used at 0, 1 and 2 percent concentration. The wet ~LLenyLI-agent was MARVESIN T35AS - a polyamide-amine-epichlorohydrin resin - at concentrations of 2, 4 and 6 percent. The test mztrix were thus as follows in Table 1.1.
The resultant wet strength peLuu-.L~ges are presented in Table 1.2.
These results are also illustrated graphically in Figures 1.1, 1.2 and 1.3.
The wet strength increa5ed almost linearly wlth the increase in quantlty of the wet ~LLenyLll agent, and the anlonic contaminants, not surprisingly, ~1m~n~h the ef~ect of the wet ~LenyLll agent. However, by the additlon of ZEûPAC VP1, this reduction in wet ~LLUI1YL1I can be curbed, and the composite of the invention is thus , , cating for the disadvantageous effect of the contaminant present.
DRY CûNTENT, pH and CATIONIC CHARGE
The dry content was determined after drying composites of the invention for three hours at 80~C at 1 atmosphere. The pH was measured immediately after production of a g~ ZEûPAC
aqueous sllcp~nci~n and 30 minutes thereafter.
WOgCt34~4 ~ 83q PCTtAU9C~261 T h e c ati o n i c c h a r g e was d e te r m i n e d b y polyelectrolytetitratlon (~'ET).
The appropriate parameters are given in Table 2.l.
The cationic surface charge in ac~n~n3 order is ZEOPAC 4, ZEOPAC l, ZEOPAC 2, ZEOPAC 3.
Sieve filtrates from paper production were analyzed for dissolved electrolytes with and without ZEOPAC l to ZEOPAC
4. The results of the PET and the conductivity mea~uL~ L~ are presented in Table 2.2.
ZEOPAC l, ZEOPAC 2 and ZEC)PAC 3 have a similar effect on the decrease of titratable anions in the filtrates, with ZEOPAC 4 exhibiting a slightly weaker effect.
CONCENTRATION OF ZEOPAC
ZEOPAC l was selected to determine the influence of ZEOPAC
dose rates. The results are presented in Table 3 and depicted in Figure 2.
GUMMING TESTS
A commercial gum (Reysize S30C) ~7~) and aluminium sulphate ~4~) were added to the afo,~- L~oned pulp and the effect of ZEOPAC 1 at O,l and 2% c~-1uunLLaLions was det~r~ln~d.
The results are presented in Table 4 and illustrated in Figures 3 and 4.
As the concentration of anionic contaminants increases, the performance of the sizing agent decreases. However, upcn the addition of ZEOPAC l, the performance of the sizing agent is restored as reflected in the better COBB values.
It should be noted that these i uv, ts are reflected W096/34~ ~1 qf ~S3 'j PCT1~U96~00261 not only on the sieve side but also on the upper side of the paper page. The ~h~mir~l oxygen deficiency [CSS1 also decreases upon the addition of ZEOPAC l.
~r~ollv~ DOSE OF ZEOPAC l IN PRESENCE OF A FLOCRING AGENT
The effect on anionic charge when using ZEOPAC l, with or without the presence of a flocking agent, was tested at 0, 0.8, l.6 and 3.8% concentration of ZEOPAC l. The results are presented in Table 5 and illustrated in Fisure 5.
As can be seen, the anionic charge level is lower in the presence of ZEOPAC l.
PLANT TRIAL l - PAPER PRODUCTION
The effect of composites of the present invention on the produot of "fresh" paper from 100% "recycled" paper was detprm~npfl. The results of introducing l~ ZEOPAC are presented in Table 6.
PLANT TRIAL 2 - ~ODu~llON OF WATER-PROOF CREPE
Hygiene papers were ~L~paL~d from 100% recycled paper.
The effect of introducing 0.3% ZEOPAC in the process is presented in Table 7.
As ZEOPAC is inL~oduced into the production, the quantity o~ wet strength agent required is reduced by approximately 20% but the wet breakin~ ~L'~-~L1. is maintained. There is also a significant financial saving on the cost of production.
O WO 96134684 ~ 3 9 PCrlAU96100261 The results are presented in Table 8. The introduction of ZEOPAC saw a reduction in gumming contaminants, a reduction in the amount of sizing agent required, but maintaining the COBB value. Once again, a significant cost saving ln plodu~ion was evident.
Similar to Plant Trial 3 described above, the effect of ZEOPAC in the production of newspaper print from 100%
recycled paper was determined. The results are presented in Table 9.
The COBB value can be maintained at lower concentrations of sizing and gumming agents.
Table 10 presents the results whereb~ 10 or 15 kilograms of ZEOPAC were added per tonne of a fibrous suspension containing de-lnked waste paper. The pulp o~--o~.lLL~tion was 1% by weight. A 2~ solution of cationic size was added at 70 kg per tonne of pulp, followed by a 10 solution of aluminlum sulphate at 30 kg per tonne of pulp.
Paper sheets of weight 75g/m2 were prepared. The effect of the size on the paper was determined by measuring its COBB value. The anionic charge of the paper suspension was detPrminP~ by PET using a Streaming Current Detector (SCD).
Table 11 presents the results whereby 10 kilograms o~
ZEOPAC were added per tonne of a fibrous suspension containing de-inked waste paper. The pulp concentration W096~4684 ~ 3 9 PCT/AU96~0~fil was 1~ by weight. A 1% solution of polyamide-polyamine-epichlorohydrin was added at 60kg per tonne of pulp.
Sheets of paper of weight 75gJm2 were prepared and their wet ~L-~nyLI- determined. The rhPmim~l oxygen demand of the white water was determined by the method of Dr Lange.
Table 12 presents the results whereby 2.5, 5, 10 or lS
kilograms of ZEOPAC were added per tonne to a fibre suspcnsion pulp containing coated waste paper. The pulp concentration was 0.2~ by weight. After 10 minutes mixing, the suspension was drained. The anionic charge of the white water wa~ determ;nP~ by PET with a SCD.
Table 13 presents the results of adding 10 kilograms of ZEOPAC or talcum per tonne of waste paper pulp (comprising 70% newspaper and 30~ magazines). The ~on~nLLaLlon o~ the suspension was 15% by weight. After the addition, ~odium hydroxide solution ~50%) was added at llkg per tonne, fol Inwe~ by sodium silicate at 20kg per tonne. A fatty acid (4kg per tonne) and hydr~n peroxide (12kg per tonne of a 15~ solution) were then added. After 15 minutes mlxins, the su~p~nc~on was diluted to l~ and the sl~cpPncJ~n held in a de-inking flotation cell for 10 minutes at 35-C.
Sheets of paper with a weight of 70g/m2 were prepared from this de-inked material and tested for whiteness, ash content and presence of undesired flecks. The anionic charge of the white water was also detPr~ln~d by PET with a SCD.
~ WO96~468J 2 1 3 ' ' 3 9 PCTIAU9G/00261 EXAMP~E 5 Figur~s 6 and 7 illustrat~ the si~nificant effect ZEOPAC
has on the ~nionic contaminant levels of ground wood pulp filtrate and "recycled" paper filtrate respectively, when compared to currently availa~le zeolites 1,2, 3 and 4.
WO 96134684 f ~ , 3 ,~ P~/ATJ961002~H
Table 1.1 (Test No) Wet Strength Agent %
Anionic Contaminant 2 4 6 O ~mol/g fibre (1) (4) (7) 2 ~mol/g fibre t2) (5) ~8 4 ~mol/g fibre (3) (6) (9~
Table 1.2 Test No Wet Strength %
WSl 12.7 WS2 12.6 WS3 6.~
WS4 16.2 WS5 12.5 WS6 14.2 WS7 18.9 WS8 19.4 WS9 19.0 Table 2.1 Test Dry pH Value Cationic Content ~ Charge Immediate After 30 ~mol/5 ZEOPAC 1 97 4.24.2 1.76 ZEOPAC 2 97 4.03.9 2.19 zEOPAC 3 96 3.83.8 2.49 ZEOPAC 4 98 4.24.1 0.47 ~W096~468419 2 ! ~ 3 ~ 3 ~ PCT/AU96,00261 Table 2.2 Dose Anionic Charge Conductivity ~ mol/g fibre mS/cm ~% 6.1 5 04 1% ZEOPAC 1 3.9 4.92 1% ZEOPAC 2 4.0 4.89 1% ZEOPAC 3 3.8 4.92 1% ZEOPAC 4 4.6 4.89 Ta-)le 3 Dose Anionic Charge (% ZEOPAC) ~ mol/g iibre 0 6.1 0.5 5 1 3.9 2 3.1 Table ~
Cobb~, g/m2 Anionic CSP Conduct-Charge ivity % ZEOPAC 1 Cobb - Cobb - ~ mol/g mg/l mS/cm Sieve Uppe~
Side Side O 50 40 3.0 2240 4.40 1 43 32 2.1 2080 4.31 2 42 31 1.8 2000 4.31 Tab:Le 5 Anionic Charge ~ m~l/g % ZEOPAC 1 Without Flocking With Elocking Agent Agent o 115 96 0.8 102 74 1.6 83 3.8 7~ _ ,~ 1. y 5 ~ J 1'~
WO 9~84 PcTl~TT- -I
Tab e 6 Parameter ¦ Standard With 1% ¦ With 1~
¦ Production ZEOPAC¦ ZEOPaC VP 1 Submitted : 100% recycled paper Yield : Approximately 85% ~Approx. 15% rejected~
PM Rate : 220 m min Steam Pressure : 2.2 bar Production in m2 per 24 hrs : 725475 Production23.577 24.666 26.117 Tonnes 24 hrs Surfaae 32. 5 34 36 Weight g/m2 Moisture ~ 6.5 6.0 5.0 Total 46.0 52.0 60.0 Retention %
Ash 27.0 31.5 40.0 Rentention ~
Dry Content 37 41 43 Sludge %
Sludge Tonnes 5.0 3.1 2.3 24 hrs CSB 1 mg lt3,050 2,600 2,400 Yield ~ 63.0 66.2 70.8 ~WOg6/34684 2 1 3 1~ 3 ~ PCT/AI~g6100261 r c~ o c43 ,,. , ~ o Cq U o o o o N N
{~
U
rl, r~ o U E~
t~ _l r Q.
~ C1 . ,~, O
t' ~ O O C3 _I - O
.0 .0 ~ E~ r~
o O
~
r~ ~
I E~ ~ O
,~
g U O ~ o r C ~
~ ~ 'D C ~ ~ ~ ~ J 1:~
Tahle 9 Glue L/TonneAlum. SulphateCOBB Production Cost Cost ZEOPAC Saving per L/Tonne per ~our per Tonne (Tonnes) Tonne r-~
Without ZEOPAC ~,~
170 450 68/53 2.6 73 ~'-With 0.3 ZEOPAC
130 350 65/52 2.6 56 6.90 10.10 Table 10 Test No ZEOPAC COBB COBB Anionic Charge Ash Content kg/tonne screen sideother side ~ mol/g 1 0 34 30 7,5 7.0 2 10 29 27 5.3 7.6 3 15 29 26 4.7 7.9 7 1 -;.) 7~ Q 3 ~
E
U ~ Y ~'1 U ~, ~ ~4 ~ E
.r h .C
U ~ N O
,~ E ,, C~ o Ui C ~ ~. '~
~ O O O
.C
--I o N N N
C ~ o O O tO
~ ~ O c~ O m ~ o O ~
3 ~ ~ ,~ o o~
o o o ~ o ,~,, o N ~ ~0 ~ _I N C~ ~ U'1 .
O. O O O
N
O
~ N ~t E~
~1t~
WO~/34~4 ~ tj_ , ptCT/AU9~002t51 0 Due to the large surface area of the composites of the present invention, together with lts cationic charge, anionic contaminants can be bound to the composite. With the high retention rate pt~qc~hl~, the contamlnants are S removed to become in~uL~o,~Lud into the paper product.
Further, due to the cationic charge, the composites of the invention are not simply loosely attached to the cellulose fibre of the paper, but a hYdLUYUn bond is formed to the cellulose fibre. In effect, the composites which are thus used as a filler in paper production are firmly ~mht~ t in the fibre structure thereof thus qi~nificAntly reducing dust formation.
The composites also exhibit a high bacteriostatic effect as the protein shell of any miuLuuLy~l~ism is dissolved on contact. ûnce again, the composites with its bacterial contaminants are inc~L~vL~ted into the final paper product.
As the composites and the contaminants function as a filler in the paper production, the quantity of additional fillers required is thus reduced with a conoomitant reduction in the paper manufacturing costs.
Contaminants which affect the Cû33 value are also removed, and thus reduce the quantities of sizing agents required.
Thus, by using the present invention to remove contaminants, it achieves simultaneously a retention increase, an increase of the dry oontent of the paper prior to drying, the removal of solid substances from the water, the reduction of dissolved colloidal contaminants as well as a reduction in the number of microorganisms and other contaminants likely to be present in any waste water to be discharged from the msnufacturing plant.
~ W096~4684 2 1 ~ 3, 3 q PCT/A~96/00261 In summary, the use of composites of the present invention is both ecologically and e~.~n~ ly ~ as it leads to production increase, reduction of sludge generation, reductlon of contaminant load, reduction in ~hPm1q~l oxygen deficienCy and a cost saving.
It will be appreciated that the above examples are illustrative only of the present invention and that )~1f~ation and alterations can be made thereto without departlng from the inventive concept as defined in the following claims.
ZEOPAC l, ZEOPAC 2 and ZEC)PAC 3 have a similar effect on the decrease of titratable anions in the filtrates, with ZEOPAC 4 exhibiting a slightly weaker effect.
CONCENTRATION OF ZEOPAC
ZEOPAC l was selected to determine the influence of ZEOPAC
dose rates. The results are presented in Table 3 and depicted in Figure 2.
GUMMING TESTS
A commercial gum (Reysize S30C) ~7~) and aluminium sulphate ~4~) were added to the afo,~- L~oned pulp and the effect of ZEOPAC 1 at O,l and 2% c~-1uunLLaLions was det~r~ln~d.
The results are presented in Table 4 and illustrated in Figures 3 and 4.
As the concentration of anionic contaminants increases, the performance of the sizing agent decreases. However, upcn the addition of ZEOPAC l, the performance of the sizing agent is restored as reflected in the better COBB values.
It should be noted that these i uv, ts are reflected W096/34~ ~1 qf ~S3 'j PCT1~U96~00261 not only on the sieve side but also on the upper side of the paper page. The ~h~mir~l oxygen deficiency [CSS1 also decreases upon the addition of ZEOPAC l.
~r~ollv~ DOSE OF ZEOPAC l IN PRESENCE OF A FLOCRING AGENT
The effect on anionic charge when using ZEOPAC l, with or without the presence of a flocking agent, was tested at 0, 0.8, l.6 and 3.8% concentration of ZEOPAC l. The results are presented in Table 5 and illustrated in Fisure 5.
As can be seen, the anionic charge level is lower in the presence of ZEOPAC l.
PLANT TRIAL l - PAPER PRODUCTION
The effect of composites of the present invention on the produot of "fresh" paper from 100% "recycled" paper was detprm~npfl. The results of introducing l~ ZEOPAC are presented in Table 6.
PLANT TRIAL 2 - ~ODu~llON OF WATER-PROOF CREPE
Hygiene papers were ~L~paL~d from 100% recycled paper.
The effect of introducing 0.3% ZEOPAC in the process is presented in Table 7.
As ZEOPAC is inL~oduced into the production, the quantity o~ wet strength agent required is reduced by approximately 20% but the wet breakin~ ~L'~-~L1. is maintained. There is also a significant financial saving on the cost of production.
O WO 96134684 ~ 3 9 PCrlAU96100261 The results are presented in Table 8. The introduction of ZEOPAC saw a reduction in gumming contaminants, a reduction in the amount of sizing agent required, but maintaining the COBB value. Once again, a significant cost saving ln plodu~ion was evident.
Similar to Plant Trial 3 described above, the effect of ZEOPAC in the production of newspaper print from 100%
recycled paper was determined. The results are presented in Table 9.
The COBB value can be maintained at lower concentrations of sizing and gumming agents.
Table 10 presents the results whereb~ 10 or 15 kilograms of ZEOPAC were added per tonne of a fibrous suspension containing de-lnked waste paper. The pulp o~--o~.lLL~tion was 1% by weight. A 2~ solution of cationic size was added at 70 kg per tonne of pulp, followed by a 10 solution of aluminlum sulphate at 30 kg per tonne of pulp.
Paper sheets of weight 75g/m2 were prepared. The effect of the size on the paper was determined by measuring its COBB value. The anionic charge of the paper suspension was detPrminP~ by PET using a Streaming Current Detector (SCD).
Table 11 presents the results whereby 10 kilograms o~
ZEOPAC were added per tonne of a fibrous suspension containing de-inked waste paper. The pulp concentration W096~4684 ~ 3 9 PCT/AU96~0~fil was 1~ by weight. A 1% solution of polyamide-polyamine-epichlorohydrin was added at 60kg per tonne of pulp.
Sheets of paper of weight 75gJm2 were prepared and their wet ~L-~nyLI- determined. The rhPmim~l oxygen demand of the white water was determined by the method of Dr Lange.
Table 12 presents the results whereby 2.5, 5, 10 or lS
kilograms of ZEOPAC were added per tonne to a fibre suspcnsion pulp containing coated waste paper. The pulp concentration was 0.2~ by weight. After 10 minutes mixing, the suspension was drained. The anionic charge of the white water wa~ determ;nP~ by PET with a SCD.
Table 13 presents the results of adding 10 kilograms of ZEOPAC or talcum per tonne of waste paper pulp (comprising 70% newspaper and 30~ magazines). The ~on~nLLaLlon o~ the suspension was 15% by weight. After the addition, ~odium hydroxide solution ~50%) was added at llkg per tonne, fol Inwe~ by sodium silicate at 20kg per tonne. A fatty acid (4kg per tonne) and hydr~n peroxide (12kg per tonne of a 15~ solution) were then added. After 15 minutes mlxins, the su~p~nc~on was diluted to l~ and the sl~cpPncJ~n held in a de-inking flotation cell for 10 minutes at 35-C.
Sheets of paper with a weight of 70g/m2 were prepared from this de-inked material and tested for whiteness, ash content and presence of undesired flecks. The anionic charge of the white water was also detPr~ln~d by PET with a SCD.
~ WO96~468J 2 1 3 ' ' 3 9 PCTIAU9G/00261 EXAMP~E 5 Figur~s 6 and 7 illustrat~ the si~nificant effect ZEOPAC
has on the ~nionic contaminant levels of ground wood pulp filtrate and "recycled" paper filtrate respectively, when compared to currently availa~le zeolites 1,2, 3 and 4.
WO 96134684 f ~ , 3 ,~ P~/ATJ961002~H
Table 1.1 (Test No) Wet Strength Agent %
Anionic Contaminant 2 4 6 O ~mol/g fibre (1) (4) (7) 2 ~mol/g fibre t2) (5) ~8 4 ~mol/g fibre (3) (6) (9~
Table 1.2 Test No Wet Strength %
WSl 12.7 WS2 12.6 WS3 6.~
WS4 16.2 WS5 12.5 WS6 14.2 WS7 18.9 WS8 19.4 WS9 19.0 Table 2.1 Test Dry pH Value Cationic Content ~ Charge Immediate After 30 ~mol/5 ZEOPAC 1 97 4.24.2 1.76 ZEOPAC 2 97 4.03.9 2.19 zEOPAC 3 96 3.83.8 2.49 ZEOPAC 4 98 4.24.1 0.47 ~W096~468419 2 ! ~ 3 ~ 3 ~ PCT/AU96,00261 Table 2.2 Dose Anionic Charge Conductivity ~ mol/g fibre mS/cm ~% 6.1 5 04 1% ZEOPAC 1 3.9 4.92 1% ZEOPAC 2 4.0 4.89 1% ZEOPAC 3 3.8 4.92 1% ZEOPAC 4 4.6 4.89 Ta-)le 3 Dose Anionic Charge (% ZEOPAC) ~ mol/g iibre 0 6.1 0.5 5 1 3.9 2 3.1 Table ~
Cobb~, g/m2 Anionic CSP Conduct-Charge ivity % ZEOPAC 1 Cobb - Cobb - ~ mol/g mg/l mS/cm Sieve Uppe~
Side Side O 50 40 3.0 2240 4.40 1 43 32 2.1 2080 4.31 2 42 31 1.8 2000 4.31 Tab:Le 5 Anionic Charge ~ m~l/g % ZEOPAC 1 Without Flocking With Elocking Agent Agent o 115 96 0.8 102 74 1.6 83 3.8 7~ _ ,~ 1. y 5 ~ J 1'~
WO 9~84 PcTl~TT- -I
Tab e 6 Parameter ¦ Standard With 1% ¦ With 1~
¦ Production ZEOPAC¦ ZEOPaC VP 1 Submitted : 100% recycled paper Yield : Approximately 85% ~Approx. 15% rejected~
PM Rate : 220 m min Steam Pressure : 2.2 bar Production in m2 per 24 hrs : 725475 Production23.577 24.666 26.117 Tonnes 24 hrs Surfaae 32. 5 34 36 Weight g/m2 Moisture ~ 6.5 6.0 5.0 Total 46.0 52.0 60.0 Retention %
Ash 27.0 31.5 40.0 Rentention ~
Dry Content 37 41 43 Sludge %
Sludge Tonnes 5.0 3.1 2.3 24 hrs CSB 1 mg lt3,050 2,600 2,400 Yield ~ 63.0 66.2 70.8 ~WOg6/34684 2 1 3 1~ 3 ~ PCT/AI~g6100261 r c~ o c43 ,,. , ~ o Cq U o o o o N N
{~
U
rl, r~ o U E~
t~ _l r Q.
~ C1 . ,~, O
t' ~ O O C3 _I - O
.0 .0 ~ E~ r~
o O
~
r~ ~
I E~ ~ O
,~
g U O ~ o r C ~
~ ~ 'D C ~ ~ ~ ~ J 1:~
Tahle 9 Glue L/TonneAlum. SulphateCOBB Production Cost Cost ZEOPAC Saving per L/Tonne per ~our per Tonne (Tonnes) Tonne r-~
Without ZEOPAC ~,~
170 450 68/53 2.6 73 ~'-With 0.3 ZEOPAC
130 350 65/52 2.6 56 6.90 10.10 Table 10 Test No ZEOPAC COBB COBB Anionic Charge Ash Content kg/tonne screen sideother side ~ mol/g 1 0 34 30 7,5 7.0 2 10 29 27 5.3 7.6 3 15 29 26 4.7 7.9 7 1 -;.) 7~ Q 3 ~
E
U ~ Y ~'1 U ~, ~ ~4 ~ E
.r h .C
U ~ N O
,~ E ,, C~ o Ui C ~ ~. '~
~ O O O
.C
--I o N N N
C ~ o O O tO
~ ~ O c~ O m ~ o O ~
3 ~ ~ ,~ o o~
o o o ~ o ,~,, o N ~ ~0 ~ _I N C~ ~ U'1 .
O. O O O
N
O
~ N ~t E~
~1t~
WO~/34~4 ~ tj_ , ptCT/AU9~002t51 0 Due to the large surface area of the composites of the present invention, together with lts cationic charge, anionic contaminants can be bound to the composite. With the high retention rate pt~qc~hl~, the contamlnants are S removed to become in~uL~o,~Lud into the paper product.
Further, due to the cationic charge, the composites of the invention are not simply loosely attached to the cellulose fibre of the paper, but a hYdLUYUn bond is formed to the cellulose fibre. In effect, the composites which are thus used as a filler in paper production are firmly ~mht~ t in the fibre structure thereof thus qi~nificAntly reducing dust formation.
The composites also exhibit a high bacteriostatic effect as the protein shell of any miuLuuLy~l~ism is dissolved on contact. ûnce again, the composites with its bacterial contaminants are inc~L~vL~ted into the final paper product.
As the composites and the contaminants function as a filler in the paper production, the quantity of additional fillers required is thus reduced with a conoomitant reduction in the paper manufacturing costs.
Contaminants which affect the Cû33 value are also removed, and thus reduce the quantities of sizing agents required.
Thus, by using the present invention to remove contaminants, it achieves simultaneously a retention increase, an increase of the dry oontent of the paper prior to drying, the removal of solid substances from the water, the reduction of dissolved colloidal contaminants as well as a reduction in the number of microorganisms and other contaminants likely to be present in any waste water to be discharged from the msnufacturing plant.
~ W096~4684 2 1 ~ 3, 3 q PCT/A~96/00261 In summary, the use of composites of the present invention is both ecologically and e~.~n~ ly ~ as it leads to production increase, reduction of sludge generation, reductlon of contaminant load, reduction in ~hPm1q~l oxygen deficienCy and a cost saving.
It will be appreciated that the above examples are illustrative only of the present invention and that )~1f~ation and alterations can be made thereto without departlng from the inventive concept as defined in the following claims.
Claims (26)
1. An agent for use in the removal of contaminants from water in the production of paper and related products, said agent comprising a compound of the general formula:
(ZO)nAln(OH)n-mClm or a compound of closely related empirical formula, which, optionally, has been further coated with a polymer, wherein Z is derived from an aluminosilicate material.
(ZO)nAln(OH)n-mClm or a compound of closely related empirical formula, which, optionally, has been further coated with a polymer, wherein Z is derived from an aluminosilicate material.
2. An agent as defined in Claim 1, wherein the material is a zeolite-containing mineral.
3. An agent as defined in Claim 2, wherein the zeolite content of the mineral is at least 40% by weight.
4. An agent as defined in Claim 2 or Claim 3, wherein the Si:Al ratio of the zeolite is greater than 3.
5. An agent as defined in Claim 4 wherein the quartz contact of the zeolite is not more than 5% by weight, preferably not more than 1%.
6. An agent as defined in Claim 5, wherein the zeolite is of a clinoptilolite structure.
7. An agent as defined in any one of Claims 1 to 6, wherein the coating polymer is an amide.
8. A method as defined in Claim 7, wherein the amide is a polyamide.
9. A method as defined in Claim 8, wherein the polyamide is polyacrylamide.
10. 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 a cationic agent; and 3) optionally, coating the resultant product with a polymer.
(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 a cationic agent; and 3) optionally, coating the resultant product with a polymer.
11. A method as defined in Claim 10, wherein the mineral is activated by treating with acid or by subjecting the mineral to ammonium ion exchange.
12. A method as defined in Claim 11, wherein the mineral is activated by treatment with hydrochloric acid.
13. A method as defined in any one of Claims 10 to 12, wherein the cationic agent is selected from an alumino compound, epichlorohydrin or a derivative thereof, or dicyanodiamide.
14. A method as defined in Claim 13, wherein the alumino compound is a polyaluminium salt.
15. A method as defined in Claim 14, wherein the polyaluminium salt is polyaluminiumchloride.
16. A method as defined in any one of Claims 13 to 15, wherein the ratio of mineral:alumino compound is in the range of 1:1 to 1:2 by weight.
17. A method as defined in Claim 16, wherein the ratio is 1:1.
18. A method as defined in any one of Claims 13 to 17, wherein the activated mineral and the alumino compound are heated together at a temperature which is in the range of 100 to 600°C.
19. A method as defined in Claim 18, wherein the temperature is 300°C.
20. A method as defined in Claim 13, wherein the epichlorohydrin derivative is a polymer of epichlorohydrin.
21. A method as defined in Claim 20, wherein the polymer is further mixed with an acid.
22. A method as defined in Claim 21, wherein the acid is melamine acid.
23. An agent as defined in any one of Claims 1 to 9, when prepared by a method as defined in any one of Claims 10 to 23.
24. A method of removing contaminants from water used in the production of paper and related products, said method comprising treating the water with a compound of the general formula:
(ZO)nAln(OH)n-mClm or a component of closely related empirical formula, with, optionally, has been further coated with a polymer, wherein Z is derived from an aluminosilicate material.
(ZO)nAln(OH)n-mClm or a component of closely related empirical formula, with, optionally, has been further coated with a polymer, wherein Z is derived from an aluminosilicate material.
25. Paper or related product having incorporated therein an agent as defined in any one of Claims 1 to 9.
26. Paper or related product having incorporated therein an agent as defined in any one of Claims 1 to 9, together with contaminants removed by said agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19515932-2 | 1995-05-02 | ||
| DE19515932A DE19515932C2 (en) | 1995-05-02 | 1995-05-02 | Use of a zeolite composite product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193839A1 true CA2193839A1 (en) | 1996-11-07 |
Family
ID=7760783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193839A Abandoned CA2193839A1 (en) | 1995-05-02 | 1996-05-02 | Elimination of waste materials in paper production |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0741113B1 (en) |
| JP (1) | JPH10502871A (en) |
| AT (1) | ATE204834T1 (en) |
| AU (1) | AU5490796A (en) |
| BR (1) | BR9606382A (en) |
| CA (1) | CA2193839A1 (en) |
| DE (2) | DE19515932C2 (en) |
| FI (1) | FI965239A (en) |
| NO (1) | NO965624L (en) |
| WO (1) | WO1996034684A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010245A (en) * | 2022-05-11 | 2022-09-06 | 安徽理工大学 | Chemical wastewater treating agent, preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE202007011112U1 (en) | 2007-08-09 | 2007-11-15 | Mc Technology Gmbh | Adapter plate, jack and device for connecting an electronic control with their connecting cables |
| ES2558343T3 (en) * | 2011-09-15 | 2016-02-03 | Linde Aktiengesellschaft | Oxygen treatment of water and paper pulp from paper or cardboard production |
| CN105858788A (en) * | 2016-04-28 | 2016-08-17 | 苏州望意阳环保科技有限公司 | Sewage purifying ball and preparation method thereof |
| CN109011921B (en) * | 2018-09-10 | 2021-01-15 | 杭州博大净化设备有限公司 | Efficient air filtering membrane for air filter and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1940915C3 (en) * | 1969-08-12 | 1975-06-05 | Meiji Seika Kaisha Ltd., Tokio | Process for the production of rapidly soluble and dispersible granules from a powder |
| JPS57201506A (en) * | 1981-06-03 | 1982-12-10 | Minato Sangyo Kk | Purifying agent of water |
| JPS61133140A (en) * | 1984-11-30 | 1986-06-20 | Nippon Soda Co Ltd | Composition for purifying water |
| DE3627407C2 (en) * | 1986-08-13 | 1994-05-19 | Steinbeis Temming Papier Gmbh | Process for cleaning water circuits in pulp and paper production |
| 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 |
| SE9103661D0 (en) * | 1991-12-12 | 1991-12-12 | Kemira Kemi Ab | PROCEDURES FOR PREPARING A COAGULATING CHEMICAL |
| EP0612692B1 (en) * | 1993-02-26 | 1999-01-20 | Createrra Inc. | Method for production of water purifying substances |
| US5389200A (en) * | 1993-04-26 | 1995-02-14 | Rheox, Inc. | Process for removing inorganic components that form ash on ignition and oily waste from paper during recycling |
| NL9301919A (en) * | 1993-05-27 | 1994-12-16 | Pelt & Hooykaas | Method for capturing environmentally harmful substances from material contaminated with such substances. |
| DE4408302C2 (en) * | 1994-03-11 | 1996-04-04 | Zeochem Kft | Process for the manufacture and use of a solid composite product for water treatment |
-
1995
- 1995-05-02 DE DE19515932A patent/DE19515932C2/en not_active Expired - Fee Related
-
1996
- 1996-04-26 DE DE59607558T patent/DE59607558D1/en not_active Expired - Fee Related
- 1996-04-26 AT AT96106647T patent/ATE204834T1/en not_active IP Right Cessation
- 1996-04-26 EP EP96106647A patent/EP0741113B1/en not_active Expired - Lifetime
- 1996-05-02 CA CA002193839A patent/CA2193839A1/en not_active Abandoned
- 1996-05-02 AU AU54907/96A patent/AU5490796A/en not_active Abandoned
- 1996-05-02 BR BR9606382A patent/BR9606382A/en not_active Application Discontinuation
- 1996-05-02 WO PCT/AU1996/000261 patent/WO1996034684A1/en active Application Filing
- 1996-05-02 JP JP8532861A patent/JPH10502871A/en active Pending
- 1996-12-27 FI FI965239A patent/FI965239A/en unknown
- 1996-12-30 NO NO965624A patent/NO965624L/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010245A (en) * | 2022-05-11 | 2022-09-06 | 安徽理工大学 | Chemical wastewater treating agent, preparation method and application thereof |
| CN115010245B (en) * | 2022-05-11 | 2023-09-12 | 安徽理工大学 | Chemical wastewater treatment agent, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE59607558D1 (en) | 2001-10-04 |
| EP0741113A1 (en) | 1996-11-06 |
| ATE204834T1 (en) | 2001-09-15 |
| JPH10502871A (en) | 1998-03-17 |
| AU5490796A (en) | 1996-11-21 |
| FI965239A (en) | 1997-02-26 |
| WO1996034684A1 (en) | 1996-11-07 |
| BR9606382A (en) | 1997-10-14 |
| EP0741113B1 (en) | 2001-08-29 |
| NO965624L (en) | 1997-02-25 |
| FI965239A0 (en) | 1996-12-27 |
| NO965624D0 (en) | 1996-12-30 |
| DE19515932A1 (en) | 1996-11-07 |
| DE19515932C2 (en) | 2000-09-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDC | Discontinued application reinstated | ||
| FZDE | Discontinued |