CA2186689A1 - Colloidal silica/polyelectrolyte blends for natural water clarification - Google Patents
Colloidal silica/polyelectrolyte blends for natural water clarificationInfo
- Publication number
- CA2186689A1 CA2186689A1 CA002186689A CA2186689A CA2186689A1 CA 2186689 A1 CA2186689 A1 CA 2186689A1 CA 002186689 A CA002186689 A CA 002186689A CA 2186689 A CA2186689 A CA 2186689A CA 2186689 A1 CA2186689 A1 CA 2186689A1
- Authority
- CA
- Canada
- Prior art keywords
- water
- silica
- polymer
- poly
- turbidity
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/5209—Regulation methods for flocculation or precipitation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
- D21H17/29—Starch cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
Abstract
This invention relates to the clarification of waters containing turbidity-causing components. This method comprises the addition of a stable colloidal silica suspension and water based polymeric coagulant to the turbid water. The components of the invention may be added independently, or blended together so that addition is simultaneous. The colloidal silica may also be conditioned by passing over a cationic exchange resin prior to addition of cationic polymer. The invention is also a colloidal silica containing water-soluble cationic polymer.
Description
- 2186G~9 Field of the Illvcll~,ull This invention relates to the cl~rific~tinn of waters c~.t ~ turbidity-causing components. This method comprises the ~-lrlifif n of a stable ccllo;~l silica suspension and water based polymeric coagulant to the turbid water. The c~lmpon~ntc of the invention may be S added independently, or blended together so that a~ltlition is ~ ~u~, The c~ l silica may also be c~,n-liti-)ned by passing over a catior ic eY~h~nge resin prior to addition of cationic polymer. The invention is also a col4id~l silica co..~ water-soluble cationic polymer.
Back~round of the Lvc~ull Turbidity-causing components can be any organic or illolg~uiic species of sl~ffi~ipnt 10 particle or droplet size to create a turbid, light-d~cl~ed appearance in waste waters, industrial waters, or natural waters. These turbidity-causing components can be of an inorganic nature, an organic nature, a color body, a pigment dispersion, an oil droplet, a colloidal humic m~tP.ri~l suspension, a dispersion formed from animal wastes in waters used to collect these animal wastes, sewage components, or a~Lli~ cs of any of the above in any ratio in waters of any 15 descnption thereby obtaining a turbid translucent effect.
Turbid waters are any type of waters having dispersed therein any type of turbidity-causing component, as described above, or any other type of turbidity-causing coll~ullent which might be sirnilar in effect when dispersed in these types of waters. For c~a~ le, colloidal matter of either organic or inorganic or even mixed organic and inorganic ch~a~,lcl 20 can be turbidity-causing. Such components may vary greatly in nature and concentration, but generally contain a highly anionic surface charge which causes the colloidal particles to repel one another, thus r~ .; .g d~tl ,ed in the water, rather than set~ing out in a reasu~able ti~me frame.
EY~rnplec of turbid waters include waste waters expelled from hydrocarbon ~loces~".lg plants, waste waters expelled from chemical processing plants which synth~i7e various types 5 of rubber latexes, and effluent waters expelled from various kinds of ~IOC~ g plants using - m~teri~lcCf~ g em~ ified COlll~JOnt~ 7 whichareofal~dlOcalb~nature. Further, the waste waters may be from automotive plants or ",~..l.;.,;.,g plant operations.
A common method for removal of suspended solids from various types of turbid waters is by the well-known chemical process of cl~nfic~tion The primary unit operations in 10 clarification are coagulation combined with or followed by flocc~ tinn Coagulation is defined as neutralization of the surface charge on particles or droplets dispersed in the water.
Flocculation is defined as the agglomeration or coalescence of small particles or droplets into larger particles or droplets, generally called floc.
A method of clarification usually comprises addition to the aqueous solution to be 1~ treated of certain chemicals known as coagulants, mixing of chemical additive and aqueous liquid whereby floc formabon occurs, and subsequent removal of ~is floc by a variety of methods. In some cases, the addition of a second higher molecular weight water-soluble polymer, generally known as a flocculant may aid in the formation of floc. The removal of floc may be achieved by mechanical separation means or by merely allowing forces of gravity to 20 work upon the agglomerated solids whereby a removable sludge layer is created.
- Among ~ ,LiV~ co~l~ntC for this lJw~ose are water-soluble cationic polymers.
These m~tPri~lc function by l.eull~l~g the charge on the surface of the ~el ,ed particles or droplets which awow the turbidity-causing m~tP.ri~lc present in turbid waters to ~lnmPrate or coalesce, and to settle, or float to the top of the aqueous ~9~ where they are collected and 5 removed by techniques farniliar to the those skilled in the art.
Water-soluble cationic polymers in co~ju~ iull with polyuucleal ~1,..";.,..." species for clarifying waters cr~"~ g turbidity-causing components are licclosed in U. S. Patent No.
4,655,934 ThereactionproductsofphenoLform~ Phydeandlowlllolec~ rweight polyarnines useful for re.,l(~vlllg turbidity from low turbidity intlllctri~l waste waters are disclosedinU S PatentNo.4,308,149 Combinations of silica and polymers have been (licrlosed for some applications The use of polymeric coagulants and aqueous colloidal silica sol for paint det~rl~ific~hrln is disclosed in U S. Patent Nos. 4,863,615; 5,004,SS0 and 4,153,548. A treatment of cationic coagulant, flocculant and colloidal silica was found to enhance the d~wal~lillg of paper in U. S.
1 ~ Patent No. 4,795,531. However, none of these patents disclose mP.thrrlc for the rednc.tirln of turbidity, or compositions of colloidal silica blended with cationic polymers.
Summary of the Invenbon This invention relates to the clarification of waters cr"~t~ g turbidity-causing components. This method compnses the addition of a stable colloidal silica ~us~ ioll and 20 water based polymeric coagulant to the turbid water. The components of the invention may be added independently, or blended together so that ~ ihrJn is ~ p~ous The colloidal silica 2181~!i89 .
may also be cQn-litir,n~d by passing over a cationic ~ ~e resin prior to q~ itirln of cationic polymer. The term cnntlitinn~d as used herein refers to the act of passing the c411~ 1ql silica over a cationic eYrhqnge resin. The invention is also a c~ llr:~ql silica c~ .g water-soluble cationic polymer.
Description of the Invention The cationic water-soluble polymer inr~ rc any water-soluble polymer which carries or is capable of carrying a cationic charge when dissolved in water, whether or not that charge-callying capacity is dependent upon pH. The cationic water-soluble polymer may be poly(diallyldimethyl qmm~nium chloride), copolyrners c~ diallyldi~lyl s~
chloride and another mnnom~r, poly(epichlo~ /Lllletl~lamine), c~tir,ni7ed starch or the like. Typically, the water-soluble cationic polymers have a mr,lecnl~r weight of about 2,000 to about 2,000,000.
Aqueous colloidal silica sols are produced by the neutr~li7~tirn with d~m~t~li7~ti~n or deionization and subsequent ccnc~ntration of sodium silicate. Likewise, aqueous colloidal silica sols can be produced by the hydrolysis of alkoxy silanes. The starting aqueous silica sol can range from 20 to 60 percent by weight of discrete, dense colloidal particles of amorphous silica. Typical commercial silica sols are those set forth below in Table I. The products listed below are all commercially available from Nalco Chemical Company, One Nalco Center, Naperville, IL 60563-1198. One method of the m~nllf~chlre of the silica sols is set forth and described in U.S. Patent No. 3,901,992, which is incorporated herein by r~r~l~nce.
2186~89 TABLE I
Specific Particle Size SilicaSol % Silica Gravity (nn) pH
A 15 1.100 ~ 10.4 B - 30 1.21 ~ 10.0 C 30 1.20 ,_, 13 10.2 D 40 1.30 - -15 9.7 E 50 1.39 20 9.0 F 50 ~ ' ~ ' '~ -I-.39'' ' ~ ''~~ ' 60-- ' ' 8.5 G 40 1.30 80 8.4 H 14.5 1.10 5 9.0 1.29 20 9.3 J 34 1.23 20 3.0 S Aqueous silica sol ~,l~ili,~ioll byplacing ~"li~,a ~,u}~, in ~ Wil~l strong acid-cationic exchange resins are disclosed in U, S Pa,t,,e,n,t Nos. 3,8,67 3,Q4,,3,855,145 and 3,822,216, which are hereby incorporated by refererlce.-The invention is a method for cl~iryillg water c~ g turbidity-causing components which compnses:
a) adding to said water (i) an effective turbidity reducing arnount of an aqueous colloidal silica sol with an average particle size within the range from 1 to 150 nm and, subsequently (ii) an effechve turbidity-reducing amount of a water-soluble polymeric I S coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000, 21866~39 (b) rni~nng said collr ;~i~l silica, said coagulant and said water with a "~rl~ r~l stirring device for ~llffiri~nt time to allow flncc~ inn of the turbidity- causing components; and then, - (c) separating the flocclll~ted turbidity-causing ~-~ llb from the water to obtain rl~rified water.
The mel~h~nical stirring device may be a reactor ~ B a stirrer, a darifier, bends in piping or in-line stirrers in piping.
In another embodiment, the invention is a method for cla,~yi-lg water cn,.~ .;.lg turbidity-causing components which comprises:
a) adding to said water i) an effective turbidity--reducing amount of an aqueous cc-n-lib- ned colloidalsilica sol with an average particle size within the range of from 1 to 150 nm wherein the aqueous colloidal silica sol is cnn~ibrlned by cnnt~cting said sol with a strong acid cation exchange resin, blended with ii) an effective turbidity-reducing arnount of a water-soluble polymeric coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000;
b) mixing the colloidal silica/polymer blend with said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity-causing components; and then, c) s~a~ lg the flocc~ ted turbidity-causing cu~on~llb from the water to obtain rl~rifiP~d water.
The invention in another embodiment is a cu~u~ilion of matter ~""l" ;~ g a) an aqueous colloidal silica sol with an average particle size within the range of from 1 to 150 nm, and b) a water-soluble cationic polymer having a molecular weight within the range of from about 2,000 to about 2,000,000 splp~cted from the group ~ ;c~ of poly(diallyl dimethyl ~mmonium c~loride), poly(diallyl dh~ yl ;..,",.n.,;~ ch1~)ri.1e/acrylic acid), poly(epichlû,ohyd,i,./dimethyl ~mine), poly(ethylene dichloride/~mmoni~) and l O cationized starch, wherein the water-soluble cationic pûlymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
Altematively, the invention is a composition of matter Co~ illg:
a) an aqueous conditioned silica sol with an average parhch size within the range of from I to 150 nm wherein the silica sol is conditioned by c~-nt~-ting said sol with a l ~ strong acid cationic exch~nge resin, blended with b) a water-soluble cationic polymer having a molecular weight within the range of about 2,000 to about 2,000,000 selected from the group culL~ lg of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ;.~ ;Ulll chloTide/acrylic acid), poly(epichlorohydrin/dimethyl amine), and c~ti~mi7ed starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1. A method of producing c~ti~ni7ed starch is tli~close-l In U. S.
Patent No. 4,568,721 which is hereby illcolllulal~d by l~reledlce. The cationic ge resin is pre-treated with an acid s~ tir n Typical soluti- nc are aqueous collltirnc of acids such as HN03, H2SO4 and HCl. After passing the silica through the cationic ~Yr'n~nge resin, an ~propliate water-soluble cationic polymer is blended with the eY~h~nged colloidal silica solution.
The invention in another embodiment is a process for pr~i lg a silica sol/water-soluble cationic polymer mixture which c~ ;c~c the steps of:
a) blending an aqueous cr~n~liht-ned silica sol with an average particle size within the range of from I to 150 nm wherein the silica sol is c~n-litirn~d by c~nt~cting said sol with a strong acid cationic exchange resin with b) a water-soluble cationic polymer having a mr~leclll~r weight within the range of from about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ~mmnnium chloride), poly(diallyl dimethyl ~mmnni~m chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), poly(ethylene fli~loride/~mmrni~) and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
In any of the embodiments, the water-soluble polymeric coagulant is selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(epichlorohyd dimethylamine), poly(ethylene dichloride/arnmonia), poly(diallyl dimethyl ~
20 chlonde/acrylic acid) and cationized starch. The weight ratio of the silica sol to the water-.
.
soluble polymeric coagulant is from 100:1 to 1:1, l~crc~ly from 50:1 to 2:1 and mostprcrcl~bly from 25:1 to 5:1.
Moreover, water-soluble polymer flocc~ ntc which may be used in conjunction with the coagulant/silica sol compositions described herein can be vinylic polymers cn..~i1;..;..E at 5 least l O mer percent of a cationic m~nnm~r chosen from the group con~ of; allylamine, dimethylaminoethylmethacrylate, dimethylamino c~yh..~ ylate qn~t.o.rni7ed with dilllc~lyl sulfate, diallyl cyclr~hPYohe~ylamine hydrochlnritle, diallyl ~lilllcLyl ~.llllln~ chl~ le, dimethyl aminoethyl acrylate and /or its acid salts, c1L~Iyl~mitl.~u~yl ~ c~lyl ~mmnnillm chloride, I-acrylamido-4-methyl piperazine qll~ d with methyl~hlnrirle, or dimethyl 10 sulfate, diethylaminoethyl acrylate and/or its acids salts, diethyl~minnethyl methacrylate and/or its acid salts, dimethylaminoethyl acrylamide and/or its acid salts, dhllc~ylaminoethyl methylacrylamide and/or its acid salts, diethylaminoethyl acrylamide and/or its acid salts, diethylaminoethyl methacrylamide and/or its acid salts, and ~f~ cs thereof. The turbidity-causing components are suspended solids and dispersed or emulsified oils and grease, among 15 others. Dosages are dependant upon the type of turbidity-causing components and the type of water treated. Silica may be treated in from about 0.25 to about 2,000 mg/L and cationic polymer may also be treated in from about 0.25 to about 2,000 mg/L.
The following examples are presented to describe preferred embodim~ntc and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims 20 appended hereto.
Example 1 Water to be treated was obtained from a mi~lwc~lc,,, river. A standard jar test procedure was pclr~ ed using a Phipps and Bird 6 station unit witb light box for mixing. To a 1000 rnl jar was added 500 ml of waste water. Subsequently 0.1 ml of a 15% by weight 5 colloidal silica was added to the jar and mixed for one minute at 100 rpm. Then 0.1 ml of an epichlolo~dlill/dimethylamine copolymer solution [poly(epi/DMA)] polymer at 0.5% actives was added to the jar and mixed for one minute at 100 rpm. The order of addition of the silica and polyelectrolyte is significant as greater activity is dr.~ tcd when silica is added before the polyelectrolyte. Next, the treated waste water solution was mixed slowly at 30 rmp for 15 10 rninutes, followed by 15 rninutes without stirring to allow the floc to seffle to the bottom of the jar.
After settling, 25 mls were drawn offofthe top of each sample with a syringe. The turbidity of this aliquot was measured using a Hach P2100 turbidimlotçr Residual silica was determined by ICP analysis.
The results are shown in Table II for river water (also referred to as a raw water). The colloidal silicalpoly(epi-DMA) treatment of this invention produces results co~ ble to that of the conventional polyaluminum chloride treatment without significantly illClc~sillg residual aluminum in solution. By decreasing the amount of soluble all...li~lll.-- fouling of ion exchange resins in demineralizer systems and membranes in reverse osmosis systerns in dowll~
20 water treatment processes is reduced. Also, the invention does not produce as much residual silica as conventional treatments. The results may be coll~ cd to those obtained for sodium silicate, which causes an i~ ea~e in residual silica and is not as ~ in turbidity reductinn - TABLE II
Turbidib Removall in Municipal Waste Water Treatment Dosage ¦ Epi/DMA Polymer Treatment I (ppm) ¦ Dosage(ppm) ¦ Turbidiity(NllJ) ¦ Residual Si (ppm) Polyalllminllm 20 _ 13.6 5.1 Chloride poly~i 25 -- 10.7 5.5 Chlonde polyAlllminllm 30 8.70 5.2 Chloride Polysil 35 -- 7.09 5.3 Chlonde Polysilllmimlm 40 -- 5.51 5.1 Chloride Polyaluminum 45 -- 4.13 5.3 Chloride Co o ca ca2 : ~ 2 Co o ca caZ n Co o c~a ca2 ~ n,~
Co o c~a 2 ~ .'.U 1~"
Co o ca - ca2 ~ ~ ~,n 6._ Co o c a ca2 ,o~ um cate~ 2 u ~': .9 o~ um cate' : . ~ 7 o~ um cate3 ~ ~ 7 oc um cate~ 11.6 ~ ~.0 22.4 51.4 1 4.2 I =pH=807 ' = 15% Actives ~ = 29 2% Actives 10 ExamPle 2 The experimental procedure described in Example I was utilized to obtain the results shown in Table m In this example, the procedure was slightly modified because the coll~
silica and epi/DMA were blended together prior to addition to the raw water to be ~1sirifie~'i 21866~39 - For the blended llæ~ ln~ cnllr: l~l silica soluti~n~ in a lS percentby weight of silica wit_ an average particle ~ met~r of 4 nm are passed t_roug_ an ~mh-orlite ~-120 cationic Px~h~n~e resin available from Rohm & Haas in Ph~ p~rhi~ Pe~iylv~ia at a rate of 0.2 - rnl/min. The cationic PYrh~nge resin is plel~èaled with a 2N HNO3 solllti~n After passing the 5 silica through the cationic eY~h~nge resin, a poly(epicloloL~ ..cll~lamine) of 20,000 weight average molecular weight was blended with the a~ a~ed coll~ l silica soll~ti~ n TABLE III
Turbidity Removal Compa. of Blend to Conventional Treatment in Municipal Waste Water Poly~l m Dosagel (ppm)Chloride (NTU)Blend 12 (N'I U) Blend 23 (NTU) Blend 34 (NTU) 3.1 72.9 6.2 --- --- 68 ----9.3 --- --- 64.9 38.4 12.4 --- --- 53.5 17.5 15.5 --- --- 30 11.1 18.6 --- --- 27 10.3 21.7 --- 34.5 26.' 9.6 24.8 --- 27.8 16.3 8.62 27.9 30.2 24.9 6.69 7.3 3] 26 18.2 5.87 5.62 34.1 --- 8.39 4.03 5.22 37.2 17.9 7.35 9.38 4.73 13.3 ---44 12.2 --- ---1 = at no treatrnent, turbidity is 68.6; dosage 5 based on amount of silica 2 = 17: I weight percent ratio of colloidal silica to epi/DMA copolymer 3 = 17:2 weight percent raho of colloidal silica to epi/DMA copolyrner 4 = 17:4 weight percent ratio of colloidal silica to epi/DMA copolymer - 218~689 Example 3 The t-l,e~ ;...Pnt~l plucedu~e des~,il,ed in FY~mrle 2 was utilized to obtain the results shown in Table IV. Here, the blended ll~A~ i of FY~1e 2 were co~ ed to the dual tre~tm~.nt.c of Example 1, in a synthetic oily waste water pr~)~ed by rni~nng 0.1 rnl of castor S oil for 25 sec. with 4L of hot water. The turbidity of the P.mlllci~n was 15 NTU.
TABLE IV
Comparison of Blend to Dual Treatment for Turbidib Removal from Synthetic Oily Water Dosage ' (ppm)Blend 1Z (NTU) Blend 23 (~I U) Dual4 1.4 8.15 --- 8.54 1.6 2.8 3.32 --- 7.1 3.2 --- 12 ---3.5 3 4 4.2 --- --- 4.55 4.9 2.59 7.38 ---5.6 3.66 --- 2.86 6.4 --- 4.76 ---7 2.48 --- 2 8 --- 2.99 ---8.4 4.04 --- 2.23 9.6 --- 4.65 ---9.8 2.28 --- 2.1 11.2 3.29 5.15 ---12.6 3.77 12.8 --- 7.88 ---14 3.9 1 = at no treatment, turbidity is 16.7; dosage 5 based on amount of silica 2 = 7: I weight percent ratio of colloidal silica (A) to epi/DMA copolymer 3 = 17: I weight percent ratio of colloidal silica (J) to epi/DMA copolymer 4 = Colloidal silica and 1 ppm epi/DMA copolymer dosed independently, as described in Example 1.
~186fi89 Ch~ngec can be made in the cc lll~Jo~ilioll, opera'aon and ~~ nt of the method of - the present i~ liun described herein without d~a~ g from the concept and scope of the invention as defined in the following claims:
Back~round of the Lvc~ull Turbidity-causing components can be any organic or illolg~uiic species of sl~ffi~ipnt 10 particle or droplet size to create a turbid, light-d~cl~ed appearance in waste waters, industrial waters, or natural waters. These turbidity-causing components can be of an inorganic nature, an organic nature, a color body, a pigment dispersion, an oil droplet, a colloidal humic m~tP.ri~l suspension, a dispersion formed from animal wastes in waters used to collect these animal wastes, sewage components, or a~Lli~ cs of any of the above in any ratio in waters of any 15 descnption thereby obtaining a turbid translucent effect.
Turbid waters are any type of waters having dispersed therein any type of turbidity-causing component, as described above, or any other type of turbidity-causing coll~ullent which might be sirnilar in effect when dispersed in these types of waters. For c~a~ le, colloidal matter of either organic or inorganic or even mixed organic and inorganic ch~a~,lcl 20 can be turbidity-causing. Such components may vary greatly in nature and concentration, but generally contain a highly anionic surface charge which causes the colloidal particles to repel one another, thus r~ .; .g d~tl ,ed in the water, rather than set~ing out in a reasu~able ti~me frame.
EY~rnplec of turbid waters include waste waters expelled from hydrocarbon ~loces~".lg plants, waste waters expelled from chemical processing plants which synth~i7e various types 5 of rubber latexes, and effluent waters expelled from various kinds of ~IOC~ g plants using - m~teri~lcCf~ g em~ ified COlll~JOnt~ 7 whichareofal~dlOcalb~nature. Further, the waste waters may be from automotive plants or ",~..l.;.,;.,g plant operations.
A common method for removal of suspended solids from various types of turbid waters is by the well-known chemical process of cl~nfic~tion The primary unit operations in 10 clarification are coagulation combined with or followed by flocc~ tinn Coagulation is defined as neutralization of the surface charge on particles or droplets dispersed in the water.
Flocculation is defined as the agglomeration or coalescence of small particles or droplets into larger particles or droplets, generally called floc.
A method of clarification usually comprises addition to the aqueous solution to be 1~ treated of certain chemicals known as coagulants, mixing of chemical additive and aqueous liquid whereby floc formabon occurs, and subsequent removal of ~is floc by a variety of methods. In some cases, the addition of a second higher molecular weight water-soluble polymer, generally known as a flocculant may aid in the formation of floc. The removal of floc may be achieved by mechanical separation means or by merely allowing forces of gravity to 20 work upon the agglomerated solids whereby a removable sludge layer is created.
- Among ~ ,LiV~ co~l~ntC for this lJw~ose are water-soluble cationic polymers.
These m~tPri~lc function by l.eull~l~g the charge on the surface of the ~el ,ed particles or droplets which awow the turbidity-causing m~tP.ri~lc present in turbid waters to ~lnmPrate or coalesce, and to settle, or float to the top of the aqueous ~9~ where they are collected and 5 removed by techniques farniliar to the those skilled in the art.
Water-soluble cationic polymers in co~ju~ iull with polyuucleal ~1,..";.,..." species for clarifying waters cr~"~ g turbidity-causing components are licclosed in U. S. Patent No.
4,655,934 ThereactionproductsofphenoLform~ Phydeandlowlllolec~ rweight polyarnines useful for re.,l(~vlllg turbidity from low turbidity intlllctri~l waste waters are disclosedinU S PatentNo.4,308,149 Combinations of silica and polymers have been (licrlosed for some applications The use of polymeric coagulants and aqueous colloidal silica sol for paint det~rl~ific~hrln is disclosed in U S. Patent Nos. 4,863,615; 5,004,SS0 and 4,153,548. A treatment of cationic coagulant, flocculant and colloidal silica was found to enhance the d~wal~lillg of paper in U. S.
1 ~ Patent No. 4,795,531. However, none of these patents disclose mP.thrrlc for the rednc.tirln of turbidity, or compositions of colloidal silica blended with cationic polymers.
Summary of the Invenbon This invention relates to the clarification of waters cr"~t~ g turbidity-causing components. This method compnses the addition of a stable colloidal silica ~us~ ioll and 20 water based polymeric coagulant to the turbid water. The components of the invention may be added independently, or blended together so that ~ ihrJn is ~ p~ous The colloidal silica 2181~!i89 .
may also be cQn-litir,n~d by passing over a cationic ~ ~e resin prior to q~ itirln of cationic polymer. The term cnntlitinn~d as used herein refers to the act of passing the c411~ 1ql silica over a cationic eYrhqnge resin. The invention is also a c~ llr:~ql silica c~ .g water-soluble cationic polymer.
Description of the Invention The cationic water-soluble polymer inr~ rc any water-soluble polymer which carries or is capable of carrying a cationic charge when dissolved in water, whether or not that charge-callying capacity is dependent upon pH. The cationic water-soluble polymer may be poly(diallyldimethyl qmm~nium chloride), copolyrners c~ diallyldi~lyl s~
chloride and another mnnom~r, poly(epichlo~ /Lllletl~lamine), c~tir,ni7ed starch or the like. Typically, the water-soluble cationic polymers have a mr,lecnl~r weight of about 2,000 to about 2,000,000.
Aqueous colloidal silica sols are produced by the neutr~li7~tirn with d~m~t~li7~ti~n or deionization and subsequent ccnc~ntration of sodium silicate. Likewise, aqueous colloidal silica sols can be produced by the hydrolysis of alkoxy silanes. The starting aqueous silica sol can range from 20 to 60 percent by weight of discrete, dense colloidal particles of amorphous silica. Typical commercial silica sols are those set forth below in Table I. The products listed below are all commercially available from Nalco Chemical Company, One Nalco Center, Naperville, IL 60563-1198. One method of the m~nllf~chlre of the silica sols is set forth and described in U.S. Patent No. 3,901,992, which is incorporated herein by r~r~l~nce.
2186~89 TABLE I
Specific Particle Size SilicaSol % Silica Gravity (nn) pH
A 15 1.100 ~ 10.4 B - 30 1.21 ~ 10.0 C 30 1.20 ,_, 13 10.2 D 40 1.30 - -15 9.7 E 50 1.39 20 9.0 F 50 ~ ' ~ ' '~ -I-.39'' ' ~ ''~~ ' 60-- ' ' 8.5 G 40 1.30 80 8.4 H 14.5 1.10 5 9.0 1.29 20 9.3 J 34 1.23 20 3.0 S Aqueous silica sol ~,l~ili,~ioll byplacing ~"li~,a ~,u}~, in ~ Wil~l strong acid-cationic exchange resins are disclosed in U, S Pa,t,,e,n,t Nos. 3,8,67 3,Q4,,3,855,145 and 3,822,216, which are hereby incorporated by refererlce.-The invention is a method for cl~iryillg water c~ g turbidity-causing components which compnses:
a) adding to said water (i) an effective turbidity reducing arnount of an aqueous colloidal silica sol with an average particle size within the range from 1 to 150 nm and, subsequently (ii) an effechve turbidity-reducing amount of a water-soluble polymeric I S coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000, 21866~39 (b) rni~nng said collr ;~i~l silica, said coagulant and said water with a "~rl~ r~l stirring device for ~llffiri~nt time to allow flncc~ inn of the turbidity- causing components; and then, - (c) separating the flocclll~ted turbidity-causing ~-~ llb from the water to obtain rl~rified water.
The mel~h~nical stirring device may be a reactor ~ B a stirrer, a darifier, bends in piping or in-line stirrers in piping.
In another embodiment, the invention is a method for cla,~yi-lg water cn,.~ .;.lg turbidity-causing components which comprises:
a) adding to said water i) an effective turbidity--reducing amount of an aqueous cc-n-lib- ned colloidalsilica sol with an average particle size within the range of from 1 to 150 nm wherein the aqueous colloidal silica sol is cnn~ibrlned by cnnt~cting said sol with a strong acid cation exchange resin, blended with ii) an effective turbidity-reducing arnount of a water-soluble polymeric coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000;
b) mixing the colloidal silica/polymer blend with said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity-causing components; and then, c) s~a~ lg the flocc~ ted turbidity-causing cu~on~llb from the water to obtain rl~rifiP~d water.
The invention in another embodiment is a cu~u~ilion of matter ~""l" ;~ g a) an aqueous colloidal silica sol with an average particle size within the range of from 1 to 150 nm, and b) a water-soluble cationic polymer having a molecular weight within the range of from about 2,000 to about 2,000,000 splp~cted from the group ~ ;c~ of poly(diallyl dimethyl ~mmonium c~loride), poly(diallyl dh~ yl ;..,",.n.,;~ ch1~)ri.1e/acrylic acid), poly(epichlû,ohyd,i,./dimethyl ~mine), poly(ethylene dichloride/~mmoni~) and l O cationized starch, wherein the water-soluble cationic pûlymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
Altematively, the invention is a composition of matter Co~ illg:
a) an aqueous conditioned silica sol with an average parhch size within the range of from I to 150 nm wherein the silica sol is conditioned by c~-nt~-ting said sol with a l ~ strong acid cationic exch~nge resin, blended with b) a water-soluble cationic polymer having a molecular weight within the range of about 2,000 to about 2,000,000 selected from the group culL~ lg of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ;.~ ;Ulll chloTide/acrylic acid), poly(epichlorohydrin/dimethyl amine), and c~ti~mi7ed starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1. A method of producing c~ti~ni7ed starch is tli~close-l In U. S.
Patent No. 4,568,721 which is hereby illcolllulal~d by l~reledlce. The cationic ge resin is pre-treated with an acid s~ tir n Typical soluti- nc are aqueous collltirnc of acids such as HN03, H2SO4 and HCl. After passing the silica through the cationic ~Yr'n~nge resin, an ~propliate water-soluble cationic polymer is blended with the eY~h~nged colloidal silica solution.
The invention in another embodiment is a process for pr~i lg a silica sol/water-soluble cationic polymer mixture which c~ ;c~c the steps of:
a) blending an aqueous cr~n~liht-ned silica sol with an average particle size within the range of from I to 150 nm wherein the silica sol is c~n-litirn~d by c~nt~cting said sol with a strong acid cationic exchange resin with b) a water-soluble cationic polymer having a mr~leclll~r weight within the range of from about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ~mmnnium chloride), poly(diallyl dimethyl ~mmnni~m chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), poly(ethylene fli~loride/~mmrni~) and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
In any of the embodiments, the water-soluble polymeric coagulant is selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(epichlorohyd dimethylamine), poly(ethylene dichloride/arnmonia), poly(diallyl dimethyl ~
20 chlonde/acrylic acid) and cationized starch. The weight ratio of the silica sol to the water-.
.
soluble polymeric coagulant is from 100:1 to 1:1, l~crc~ly from 50:1 to 2:1 and mostprcrcl~bly from 25:1 to 5:1.
Moreover, water-soluble polymer flocc~ ntc which may be used in conjunction with the coagulant/silica sol compositions described herein can be vinylic polymers cn..~i1;..;..E at 5 least l O mer percent of a cationic m~nnm~r chosen from the group con~ of; allylamine, dimethylaminoethylmethacrylate, dimethylamino c~yh..~ ylate qn~t.o.rni7ed with dilllc~lyl sulfate, diallyl cyclr~hPYohe~ylamine hydrochlnritle, diallyl ~lilllcLyl ~.llllln~ chl~ le, dimethyl aminoethyl acrylate and /or its acid salts, c1L~Iyl~mitl.~u~yl ~ c~lyl ~mmnnillm chloride, I-acrylamido-4-methyl piperazine qll~ d with methyl~hlnrirle, or dimethyl 10 sulfate, diethylaminoethyl acrylate and/or its acids salts, diethyl~minnethyl methacrylate and/or its acid salts, dimethylaminoethyl acrylamide and/or its acid salts, dhllc~ylaminoethyl methylacrylamide and/or its acid salts, diethylaminoethyl acrylamide and/or its acid salts, diethylaminoethyl methacrylamide and/or its acid salts, and ~f~ cs thereof. The turbidity-causing components are suspended solids and dispersed or emulsified oils and grease, among 15 others. Dosages are dependant upon the type of turbidity-causing components and the type of water treated. Silica may be treated in from about 0.25 to about 2,000 mg/L and cationic polymer may also be treated in from about 0.25 to about 2,000 mg/L.
The following examples are presented to describe preferred embodim~ntc and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims 20 appended hereto.
Example 1 Water to be treated was obtained from a mi~lwc~lc,,, river. A standard jar test procedure was pclr~ ed using a Phipps and Bird 6 station unit witb light box for mixing. To a 1000 rnl jar was added 500 ml of waste water. Subsequently 0.1 ml of a 15% by weight 5 colloidal silica was added to the jar and mixed for one minute at 100 rpm. Then 0.1 ml of an epichlolo~dlill/dimethylamine copolymer solution [poly(epi/DMA)] polymer at 0.5% actives was added to the jar and mixed for one minute at 100 rpm. The order of addition of the silica and polyelectrolyte is significant as greater activity is dr.~ tcd when silica is added before the polyelectrolyte. Next, the treated waste water solution was mixed slowly at 30 rmp for 15 10 rninutes, followed by 15 rninutes without stirring to allow the floc to seffle to the bottom of the jar.
After settling, 25 mls were drawn offofthe top of each sample with a syringe. The turbidity of this aliquot was measured using a Hach P2100 turbidimlotçr Residual silica was determined by ICP analysis.
The results are shown in Table II for river water (also referred to as a raw water). The colloidal silicalpoly(epi-DMA) treatment of this invention produces results co~ ble to that of the conventional polyaluminum chloride treatment without significantly illClc~sillg residual aluminum in solution. By decreasing the amount of soluble all...li~lll.-- fouling of ion exchange resins in demineralizer systems and membranes in reverse osmosis systerns in dowll~
20 water treatment processes is reduced. Also, the invention does not produce as much residual silica as conventional treatments. The results may be coll~ cd to those obtained for sodium silicate, which causes an i~ ea~e in residual silica and is not as ~ in turbidity reductinn - TABLE II
Turbidib Removall in Municipal Waste Water Treatment Dosage ¦ Epi/DMA Polymer Treatment I (ppm) ¦ Dosage(ppm) ¦ Turbidiity(NllJ) ¦ Residual Si (ppm) Polyalllminllm 20 _ 13.6 5.1 Chloride poly~i 25 -- 10.7 5.5 Chlonde polyAlllminllm 30 8.70 5.2 Chloride Polysil 35 -- 7.09 5.3 Chlonde Polysilllmimlm 40 -- 5.51 5.1 Chloride Polyaluminum 45 -- 4.13 5.3 Chloride Co o ca ca2 : ~ 2 Co o ca caZ n Co o c~a ca2 ~ n,~
Co o c~a 2 ~ .'.U 1~"
Co o ca - ca2 ~ ~ ~,n 6._ Co o c a ca2 ,o~ um cate~ 2 u ~': .9 o~ um cate' : . ~ 7 o~ um cate3 ~ ~ 7 oc um cate~ 11.6 ~ ~.0 22.4 51.4 1 4.2 I =pH=807 ' = 15% Actives ~ = 29 2% Actives 10 ExamPle 2 The experimental procedure described in Example I was utilized to obtain the results shown in Table m In this example, the procedure was slightly modified because the coll~
silica and epi/DMA were blended together prior to addition to the raw water to be ~1sirifie~'i 21866~39 - For the blended llæ~ ln~ cnllr: l~l silica soluti~n~ in a lS percentby weight of silica wit_ an average particle ~ met~r of 4 nm are passed t_roug_ an ~mh-orlite ~-120 cationic Px~h~n~e resin available from Rohm & Haas in Ph~ p~rhi~ Pe~iylv~ia at a rate of 0.2 - rnl/min. The cationic PYrh~nge resin is plel~èaled with a 2N HNO3 solllti~n After passing the 5 silica through the cationic eY~h~nge resin, a poly(epicloloL~ ..cll~lamine) of 20,000 weight average molecular weight was blended with the a~ a~ed coll~ l silica soll~ti~ n TABLE III
Turbidity Removal Compa. of Blend to Conventional Treatment in Municipal Waste Water Poly~l m Dosagel (ppm)Chloride (NTU)Blend 12 (N'I U) Blend 23 (NTU) Blend 34 (NTU) 3.1 72.9 6.2 --- --- 68 ----9.3 --- --- 64.9 38.4 12.4 --- --- 53.5 17.5 15.5 --- --- 30 11.1 18.6 --- --- 27 10.3 21.7 --- 34.5 26.' 9.6 24.8 --- 27.8 16.3 8.62 27.9 30.2 24.9 6.69 7.3 3] 26 18.2 5.87 5.62 34.1 --- 8.39 4.03 5.22 37.2 17.9 7.35 9.38 4.73 13.3 ---44 12.2 --- ---1 = at no treatrnent, turbidity is 68.6; dosage 5 based on amount of silica 2 = 17: I weight percent ratio of colloidal silica to epi/DMA copolymer 3 = 17:2 weight percent raho of colloidal silica to epi/DMA copolyrner 4 = 17:4 weight percent ratio of colloidal silica to epi/DMA copolymer - 218~689 Example 3 The t-l,e~ ;...Pnt~l plucedu~e des~,il,ed in FY~mrle 2 was utilized to obtain the results shown in Table IV. Here, the blended ll~A~ i of FY~1e 2 were co~ ed to the dual tre~tm~.nt.c of Example 1, in a synthetic oily waste water pr~)~ed by rni~nng 0.1 rnl of castor S oil for 25 sec. with 4L of hot water. The turbidity of the P.mlllci~n was 15 NTU.
TABLE IV
Comparison of Blend to Dual Treatment for Turbidib Removal from Synthetic Oily Water Dosage ' (ppm)Blend 1Z (NTU) Blend 23 (~I U) Dual4 1.4 8.15 --- 8.54 1.6 2.8 3.32 --- 7.1 3.2 --- 12 ---3.5 3 4 4.2 --- --- 4.55 4.9 2.59 7.38 ---5.6 3.66 --- 2.86 6.4 --- 4.76 ---7 2.48 --- 2 8 --- 2.99 ---8.4 4.04 --- 2.23 9.6 --- 4.65 ---9.8 2.28 --- 2.1 11.2 3.29 5.15 ---12.6 3.77 12.8 --- 7.88 ---14 3.9 1 = at no treatment, turbidity is 16.7; dosage 5 based on amount of silica 2 = 7: I weight percent ratio of colloidal silica (A) to epi/DMA copolymer 3 = 17: I weight percent ratio of colloidal silica (J) to epi/DMA copolymer 4 = Colloidal silica and 1 ppm epi/DMA copolymer dosed independently, as described in Example 1.
~186fi89 Ch~ngec can be made in the cc lll~Jo~ilioll, opera'aon and ~~ nt of the method of - the present i~ liun described herein without d~a~ g from the concept and scope of the invention as defined in the following claims:
Claims (23)
1. A method for clarifying water containing turbidity-causing components which comprises:
a) adding to said water (i) an effective turbidity reducing amount of an aqueous colloidal silica sol with an average particle size within the range from 1 to 150 nm and, subsequently (ii) an effective turbidity-reducing amount of a water-soluble polymeric coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000;
(b) mixing said colloidal silica, said coagulant and said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity causing components; and then, (c) separating the flocculated turbidity-causing components from the water to obtain clarified water.
a) adding to said water (i) an effective turbidity reducing amount of an aqueous colloidal silica sol with an average particle size within the range from 1 to 150 nm and, subsequently (ii) an effective turbidity-reducing amount of a water-soluble polymeric coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000;
(b) mixing said colloidal silica, said coagulant and said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity causing components; and then, (c) separating the flocculated turbidity-causing components from the water to obtain clarified water.
2. The method of Claim 1 wherein the water-soluble polymeric coagulant is selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethylamine), poly(ethylene dichloride/ammonia) and cationized starch.
3. The method of Claim 1 wherein the turbidity-causing components are suspended solids.
4. The method of Claim 1 wherein the turbidity-causing components are oil and grease.
5. The method of Claim 1 wherein the water-soluble polymeric coagulant and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
6. The method of Claim 1 wherein the water-soluble polymeric coagulant and the silica sol are present in a weight ratio of silica to polymer of from 50:1 to 2:1.
7. The method of Claim 1 wherein the water-soluble polymeric coagulant and the silica sol are present in a weight ratio of silica to polymer of from 25:1 to 5:1.
8. A method for clarifying water containing turbidity-causing components which comprises:
a) adding to said water i) an effective turbidity-reducing amount of an aqueous conditioned colloidal silica with an average particle size within the range of from 1 to 150 nm wherein the aqueous colloidal silica sol is conditioned by contacting said sol with a strong acid cation exchange resin, blended with ii) an effective turbidity-reducing amount of a water-soluble polymeric coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000;
b) mixing the colloidal silica/polymer blend with said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity-causing components; and then, c) separating the flocculated turbidity-causing components from the water to obtain clarified water.
a) adding to said water i) an effective turbidity-reducing amount of an aqueous conditioned colloidal silica with an average particle size within the range of from 1 to 150 nm wherein the aqueous colloidal silica sol is conditioned by contacting said sol with a strong acid cation exchange resin, blended with ii) an effective turbidity-reducing amount of a water-soluble polymeric coagulant having a molecular weight within the range of from about 2,000 to about 2,000,000;
b) mixing the colloidal silica/polymer blend with said water with a mechanical stirring device for sufficient time to allow flocculation of the turbidity-causing components; and then, c) separating the flocculated turbidity-causing components from the water to obtain clarified water.
9. The method of Claim 8 wherein the water-soluble polymeric coagulant is selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethylamine), poly(ethylene dichloride/ammonia) and cationized starch.
10. The method of Claim 8 wherein the turbidity-causing components are suspended solids.
11. The method of Claim 8 wherein the turbidity-causing components are oil and grease.
12. The method of Claim 8 wherein the water-soluble polymeric coagulant and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
13. The method of Claim 8 wherein the water-soluble polymeric coagulant and the silica sol are present in a weight ratio of silica to polymer of from 50:1 to 2:1.
14. The method of Claim 8 wherein the water-soluble polymeric coagulant and the silica sol are present in a weight ratio of silica to polymer of from 25:1 to 5:1.
.
.
15. A composition of matter comprising:
a) an aqueous colloidal silica sol with an average particle size within the range of from 1 to 150 nm, and b) a water-soluble cationic polymer having a molecular weight within the range of from about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), poly(ethylene dichloride/ammonia) and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
a) an aqueous colloidal silica sol with an average particle size within the range of from 1 to 150 nm, and b) a water-soluble cationic polymer having a molecular weight within the range of from about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), poly(ethylene dichloride/ammonia) and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
16. The composition of matter according to Claim 15 wherein the weight ratio of silica to polymer is from 50:1 to 2:1.
17. The composition of matter according to Claim 15 wherein the weight ratio of silica to polymer is from 25:1 to 5:1.
18. A composition of matter comprising:
a) an aqueous conditioned silica sol with an average particle size within the range of from 1 to 150 nm wherein the silica sol is conditioned by contacting said sol with a strong acid cationic exchange resin, blended with b) a water-soluble cationic polymer having a molecular weight within the range of about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
a) an aqueous conditioned silica sol with an average particle size within the range of from 1 to 150 nm wherein the silica sol is conditioned by contacting said sol with a strong acid cationic exchange resin, blended with b) a water-soluble cationic polymer having a molecular weight within the range of about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
19. A composition of matter according to Claim 18 wherein the polymer and the silica sol are present in a weight ratio of silica to polymer of from 50:1 to 2:1.
20. A composition of matter according to Claim 18 wherein the polymer and the silica sol are present in a weight ratio of silica to polymer of from 25:1 to 5:1.
21. A process for preparing a silica sol/water-soluble cationic polymer mixture which comprises the steps of:
a) blending an aqueous conditioned silica sol with an average particle size within the range of from 1 to 150 nm wherein the silica sol is conditioned by contacting said sol with a strong acid cationic exchange resin with b) a water-soluble cationic polymer having a molecular weight within the range of from about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), poly(ethylene dichloride/ammonia) and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
a) blending an aqueous conditioned silica sol with an average particle size within the range of from 1 to 150 nm wherein the silica sol is conditioned by contacting said sol with a strong acid cationic exchange resin with b) a water-soluble cationic polymer having a molecular weight within the range of from about 2,000 to about 2,000,000 selected from the group consisting of poly(diallyl dimethyl ammonium chloride), poly(diallyl dimethyl ammonium chloride/acrylic acid), poly(epichlorohydrin/dimethyl amine), poly(ethylene dichloride/ammonia) and cationized starch, wherein the water-soluble cationic polymer and the silica sol are present in a weight ratio of silica to polymer of from 100:1 to 1:1.
22. The process of Claim 21 wherein the weight ratio of silica to polymer is from 50:1 to 2:1.
23. The process of Claim 21 wherein the weight ratio of silica to polymer is from 25:1 to 5:1.
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| US53543095A | 1995-09-28 | 1995-09-28 | |
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| EP (3) | EP0765844A1 (en) |
| KR (1) | KR970015481A (en) |
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| US5871648A (en) * | 1996-11-26 | 1999-02-16 | Environmental Chemistries, Inc. | Wastewater treatment process and apparatus for high flow impurity removal |
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| KR100385706B1 (en) * | 1997-11-06 | 2003-05-27 | 마이크로바 인코퍼레이티드 | Process for Removing Silica from Wastewater |
| EP0943632A1 (en) * | 1998-03-18 | 1999-09-22 | Ecole Polytechnique Federale De Lausanne | Quaternary ammonium polymer, its preparation, its use for separating biomolecules |
| US6132625A (en) * | 1998-05-28 | 2000-10-17 | E. I. Du Pont De Nemours And Company | Method for treatment of aqueous streams comprising biosolids |
| KR100278510B1 (en) * | 1998-08-24 | 2001-03-02 | 한성욱 | Water-soluble polymer dispersion for fine particle retention containing colloidal silica and preparation method thereof |
| KR100278507B1 (en) * | 1998-08-24 | 2001-03-02 | 한성욱 | Water-soluble polymer dispersion for wastewater treatment containing inorganic coagulant and method for producing same |
| KR20000048167A (en) * | 1998-12-24 | 2000-07-25 | 미우라 유이찌, 쓰지 가오루 | Cationic resin modified silica dispersing solution and the method for preparing the same |
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| US6203705B1 (en) | 1999-10-22 | 2001-03-20 | Koch Microelectronic Service Company, Inc. | Process for treating waste water containing copper |
| CZ299031B6 (en) * | 1999-12-20 | 2008-04-09 | Akzo Nobel N.V. | Aqueous silica-based sol, process for its preparation and use as well as process for producing paper |
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| CN102276031B (en) * | 2011-05-25 | 2013-07-17 | 童益 | Method for producing high concentration composite water purifying agent with multi-ions of aluminium, zinc and magnesian |
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| DE102013018977B4 (en) * | 2013-11-14 | 2017-04-27 | Ulrich Loser | Use of a blue algae separating agent |
| JP2020522588A (en) * | 2017-06-02 | 2020-07-30 | サウジ アラビアン オイル カンパニー | Coated silica particles |
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| US3867304A (en) * | 1967-06-12 | 1975-02-18 | Nalco Chemical Co | Acidic stable salt-free silica sols |
| US3855145A (en) * | 1971-01-28 | 1974-12-17 | Nalco Chemical Co | Preparation of concentrated silica organosols |
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| US3901992A (en) * | 1973-10-31 | 1975-08-26 | Nalco Chemical Co | Fabric for carpet and like materials containing a coating of colloidal silica with a layer of alumina |
| US4153548A (en) * | 1974-01-25 | 1979-05-08 | Nalco Chemical Company | Process for controlling pollution and contamination in the electrodeposition of paint |
| AU546999B2 (en) * | 1980-05-28 | 1985-10-03 | Eka A.B. | Adding binder to paper making stock |
| US4308149A (en) * | 1980-07-14 | 1981-12-29 | Nalco Chemical Company | Branched/cross-linked cationic phenol-formaldehyde polymers useful in wastewater treatment |
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| US4795531A (en) * | 1987-09-22 | 1989-01-03 | Nalco Chemical Company | Method for dewatering paper |
| DE68905208T3 (en) * | 1988-03-28 | 2001-02-15 | Allied Colloids Ltd | Manufacture of paper and cardboard. |
| US5004550A (en) * | 1988-08-01 | 1991-04-02 | Nalco Chemical Company | Method of paint sludge conversion for disposal |
| US4863615A (en) * | 1988-08-01 | 1989-09-05 | Nalco Chemical Company | Cationic coagulants plus collidal silica for use in paint detackification |
| SE500367C2 (en) * | 1989-11-09 | 1994-06-13 | Eka Nobel Ab | Silica soles and process for making paper |
| SE500387C2 (en) * | 1989-11-09 | 1994-06-13 | Eka Nobel Ab | Silica sols, process for making silica sols and using the soles in paper making |
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-
1995
- 1995-11-26 US US08/613,791 patent/US5620629A/en not_active Expired - Fee Related
-
1996
- 1996-08-21 US US08/701,224 patent/US5667697A/en not_active Expired - Fee Related
- 1996-09-17 AU AU65661/96A patent/AU717544B2/en not_active Ceased
- 1996-09-24 DE DE69618029T patent/DE69618029T2/en not_active Expired - Fee Related
- 1996-09-24 KR KR1019960041858A patent/KR970015481A/en not_active Application Discontinuation
- 1996-09-24 EP EP96306950A patent/EP0765844A1/en not_active Withdrawn
- 1996-09-24 ES ES99111224T patent/ES2169579T3/en not_active Expired - Lifetime
- 1996-09-24 EP EP99111224A patent/EP0952118B1/en not_active Expired - Lifetime
- 1996-09-24 EP EP99111225A patent/EP0952119A1/en not_active Withdrawn
- 1996-09-27 CA CA002186689A patent/CA2186689A1/en not_active Abandoned
- 1996-09-30 TW TW085111888A patent/TW360620B/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110894072A (en) * | 2018-09-12 | 2020-03-20 | 3S韩国株式会社 | Method for preparing synthetic quartz powder |
Also Published As
| Publication number | Publication date |
|---|---|
| TW360620B (en) | 1999-06-11 |
| KR970015481A (en) | 1997-04-28 |
| DE69618029D1 (en) | 2002-01-24 |
| EP0952118B1 (en) | 2001-12-12 |
| ES2169579T3 (en) | 2002-07-01 |
| EP0765844A1 (en) | 1997-04-02 |
| EP0952119A1 (en) | 1999-10-27 |
| EP0952118A1 (en) | 1999-10-27 |
| AU6566196A (en) | 1997-04-10 |
| DE69618029T2 (en) | 2002-07-18 |
| US5667697A (en) | 1997-09-16 |
| AU717544B2 (en) | 2000-03-30 |
| US5620629A (en) | 1997-04-15 |
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