CA1287285C - Method for flocculating suspensions containing swelled layered chalcogenide - Google Patents
Method for flocculating suspensions containing swelled layered chalcogenideInfo
- Publication number
- CA1287285C CA1287285C CA000548133A CA548133A CA1287285C CA 1287285 C CA1287285 C CA 1287285C CA 000548133 A CA000548133 A CA 000548133A CA 548133 A CA548133 A CA 548133A CA 1287285 C CA1287285 C CA 1287285C
- Authority
- CA
- Canada
- Prior art keywords
- layered
- ketone
- weight
- suspension
- parts
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 20
- 239000000725 suspension Substances 0.000 title claims abstract description 13
- 230000003311 flocculating effect Effects 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 31
- 125000002091 cationic group Chemical group 0.000 claims abstract description 18
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 230000008961 swelling Effects 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 abstract description 4
- 230000016615 flocculation Effects 0.000 abstract description 4
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 10
- -1 alkyl epoxides Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007155 step growth polymerization reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
- C01B17/18—Hydrogen polysulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/506—Method of making inorganic composition utilizing organic compound, except formic, acetic, or oxalic acid or salt thereof
- Y10S502/507—Synthetic resin, natural resin, polysaccaride, or polypeptide
Abstract
METHOD FOR FLOCCULATING SUSPENSIONS CONTAINING
SWELLED LAYERED CHALCOGENIDE
ABSTRACT
In a method of flocculating a suspension containing a) a layered oxide material intercalated with a hydrophobic swelling agent and b) nonintercalated hydrophobic swelling agent, the suspension is contacted with a ketone, water, and a cationic organic polymer. The resulting mixture is maintained at a sufficiently alkaline pH to prevent removal of the intercalated swelling agent during the flocculation treatment.
SWELLED LAYERED CHALCOGENIDE
ABSTRACT
In a method of flocculating a suspension containing a) a layered oxide material intercalated with a hydrophobic swelling agent and b) nonintercalated hydrophobic swelling agent, the suspension is contacted with a ketone, water, and a cationic organic polymer. The resulting mixture is maintained at a sufficiently alkaline pH to prevent removal of the intercalated swelling agent during the flocculation treatment.
Description
~'~87Z8~
METHOD FOR FLOCCULATING SUSPENSIONS CONTAINING
-SWELLED LAYERED CHALCOGENIDE
The present invention relates to a method for flocculating aqueous suspensions containing a swelled layered chalcogenide material.
Many layered materials are known which have three-dimensional structures which exhibit their strongest chemical bonding in only two dimensions. In such materials, the stronger chemical bonds are formed in two-dimensional planes and a three-dimensional solid is formed by stacking such planes on top of each other. However, the interactions between the planes are weaker than the chemical bonds holding an individual plane together. The weaker bonds generally arise from interlayer attractions such as Van der Waals forces, electrostatic interactions, and hydrogen bonding.
In those situations where the layered structure has electronically neutral sheets interacting with each other solely through Van der Waals forces, a high degree of lubricity is manifested as the planes slide across each other without encountering the energy barriers that arise with strong interlayer bonding. Graphite is an example of such a material. The silicate layers of a number of clay materials are held together by electrostatic attraction mediated by ions located between the layers. In addition, hydrogen bonding interactions can occur directly between complementary sites on adjacent layers, or can be mediated by interlamellar bridging molecules.
Laminated materials such as clays may be modified to increase their surface area. In particular, the interlamellar spacing can be increased substantially by absorption of various swelling agents such as water, ethylene glycol, amines and ketones, which enter the interlamellar space and push the layers apart.
~ X87X8.r;
However, the interlamellar spaces of such layered materials tend to collapse when the molecules occupying the space are removed, for example, by exposinq the clays to high temperatures. Accordingly, such layered materials having enhanced surface area are not suited for use in chemical processes involving even moderately severe conditions.
Layered metal chalcogenide materials enjoying thermal stability can be prepared by the method described in our European published Patent Application No. 0 205 711. This method comprises:
treating a layered chalcogenide, specifically an oxide, of at least one element having an atomic number of 4, 5, 12 to 15, 20 to 33, 38 to 51, 56 to 83 and greater than 90, inclusive, which contains ion exchange sites having interspathic cations associated therewith, with an organic compound which is a cationic species, e.g., n-alkylammonium or capable of forming a cationic species e.g., n-alkylamine, to effect exchange with said interspathic cations in order to swell the layered material. An electrically neutral compound capable of conversion to an interspathic polymeric oxide, e.g., tetraethylorthosilicate, is thereafter provided between the layers of the swelled, layered chalcogenide. The compound is then converted to the interspathic polymeric oxide to form the layered material.
The present invention relates to a method for filtering the layered chalcogenide which has been swelled by treatment with the above-mentioned organic compound which is either a cationic species or capable of forming a cationic species. The swelled layered material is present in an aqueous slurry or as a suspension and is ordinarily separated by means of filtration and dried before treatment with the electrically neutral compound capable of conversion to the interspathic polymeric oxide or other chalcogenide between the layers of said material. Simple filtration has been found to be time-consuming insofar as the swelled layered material is in a highly dispersed state. Accordingly, there exists a need for a method of flocculating aqueous suspensions comprising swelled layered chalcogenide materials.
- ~
~287Z~3';
F-4278 ~ 3 ~
Many flocculating agents are known, as disclosed in, for example, "Flocculating Agents," Kirk - Othmer Encyclopedia of Chemical Technology, Third Edition Volume 10, pp. 484 to 523.
Synthetic organic materials are of particular interest as flocculants. Such materials include water-soluble polymeric substances with weight average molecular weights ranging from about 103 to greater than 5X105. Where subunits of the polymer possess a positive charge, the polymer is known as a cationic organic polymeric flocculant.
These cationic polymers include polyammonium compounds such as poly(alkylene polyamines) and poly(hydroxyalkylene polyamines) which are step-growth polymerization products of polyfunctional amines and alkyl dihalides or bifunctional alkyl epoxides and alkyl epoxide derivatives. Polyamine quaternaries, another cationic polymer group are prepared by quaternization of poly(alkylene polyamines) and poly(hydroxyalkylene polyamines) with alkyl halides or sulfates or by step~growth polymerization from dialkylamines, tetraalkyl amines, or derivatives thereof, with suitable bifunctional alkylating agents, and with or without small amounts of polyfunctional primary amines. Vinyl conversion products such as cationic carbamoyl polymers are also useful as cationic flocculation agents.
The present invention relates to a method for flocculating an aqueous suspension comprising 1) a layered chalcogenide material having ion exchange sites and swelled with an intercalated hydrophobic swelling agent and 2) nonintercalated, excess hydrophobic swelling agent, which method comprises a) contacting said suspension with a ketone, water, and a cationic organic polymeric flocculant; b) maintaining the resulting mixture at a sufficiently alkaline pH to prevent exchange of said intercalated hydrophobic swelling agent; and c) separating the swelled layered chalcogenide material from the aqueous mixture, whereby said layered chalcogenide material remains swelled after the separating step.
--1~8728.S
F-4278 ~ 4 ~
It is found that the presence of a small amount of ketone solvent during flocculation with a cation:ic polymer at a controlled pH results in a dramatic improvement in filtration rates. In addition, such treatment does not destroy the integrity of the intercalated material which can therefore be treated with a hydrolyzable pillaring agent to form a thermally stable pillared product.
The floc mixture conveniently comprises 3 to lO wt.~ ketone based upon total solution and about l to 3 wt.~ of cationic organic polymer based upon actual solids in the slurry. The slurry is diluted to about 2 to 6 times the initial slurry volume using the ketone/water solution. The cationic organic polymeric flocculant is preferably added in an amount between l and 5 parts, preferably l to 3 parts by weight, compared to the weight of suspension solid.
The layered chalcogenide material employed in the present invention can be a layered oxide, sulfide, selenide or telluride, although preferably is a layered oxide material. Suitable layered oxide materials include layered oxides of Group IVA metals such as titanium, zirconium and hafnium, e.g., layered titanates such as Na2Ti307 as disclosed in U.S. Patents 4,6û0,503, and 2,496,993. Other layered chalcogenide materials in which the present invention may be used to facilitate intercalation include KTiTaO5 and Na4Mnl40279H20, as well as layered oxides of alumina and silicon such as clays, e.g. bentonite. In particular, the present invention can facilitate intercalation of layered silicates known as high silica alkali silicates whose layers lack octahedral sheets. These silicates can be prepared hydrothermally from an aqueous reaction mixture containing silica and caustic at relatively moderate temperatures and pressures, and may contain tetracoordinate framework atoms other than Si. Included among these materials are magadiite, natrosilite, kenyaite, makatite and kanemite, preferably their acid-exchanged forms.
The hydrophobic swelling agent employed in the present invention comprises a source of organic cations, such as 1287Z8.'-, F-4278 ~ 5 organoammonium cation, in order to effect an exchange of the interspathic cations resulting in the layers of the starting material being propped apart. In particular, protonated alkylamines are preferred, such as n-dodecylammonium, n-octylammonium, n-heptylammonium, n-hexylammonium and n-propylammonium cations. The source of organic cation in those instances where the interspathic cations include hydrogen or hydronium ions rnay include a neutral compound such as organic amine which is converted to a cationic analogue during the swelling or "propping" treatment. Among these materials are C3 to Clû, preferably C6 to C8 alkylamines, preferably n-alkylamines, or C3 to ClO, preferably C6 to C8 alkanols, preferably n-alkanols.
Any ketone may be used in the flocculation step which is capable of solubilizing the hydrophobic swelling agent employed.
Such ketones include C3to ClO ketones, preferably C3 to C5 ketones, e.g. methylethylketone or acetone. Preferably the ketone is added to the suspension prior to addition of the cationic organic polymeric flocculant.
The cationic organic polymeric flocculant employed preferably has a molecular weight of 5 x 105 to l x 107, more preferably l x 106 to 5 x lO6. Such materials are synthetic polyelectrolytes carrying a positive charge that serve to destabilize an emulsion by a combination of a) bridging and b) charge neutralization.
pH conditions employed in the present invention are generally sufficiently alkaline so as to prevent the formation of protons which will undesirably exchange with the protonated amine or alkanol swelling agent, resulting in collapse of the layered chalcogenide structure. Generally, the pH should be greater than 5, preferably from 9 to ll.
The invention is further described by the following Examples.
1~8728~
EXAMPLE 1 (COMPARATIVE) Twenty grams of natural magad;ite were sized to pass through a 25 mesh size screen and added to 100 ml of H20. The mixture was adjusted to a pH of about 2 and held there by addition of 0.1 N HCl within a 24 hour period. A total of 435 ml of O.lN HCl was used. The sample was filtered, water-washed and dried. The x-ray pattern of the sample showed a peak at 7.8 (2 theta) indicating an 11.3A d-spacing corresponding to the structure being in a collapsed state. The calcined sample (3 hours at 538C in air) had the same d-spacing. The adsorption properties were 27 m2/g surface area, 0.8% H20, 1.2% CyC6 and 2.0% n-C6. 5009 of an aqueous slurry containing 6759 of the acid-exchanged magadiite were treated with 16009 of n-octylamine to prop open or swell the layers. In order to recover the swelled product, lOOcc of the above slurry was subjected to vacuum filtration, a process which required more than 16 hours to recover 14gms of the swelled product.
EXAMPLE 2 (COMPARATIVE) lOOcc of the slurry described in Example 1 were mixed with 25cc of i-propyl alcohol, 375cc of water and lgm of Hercofloc~3 834, at a pH of lû. Hercofloc~ 834 is a cationic polymer which is composed of an acrylamide based copolymer with a typical viscosity range of 50,000 to 100,000 cps, sold by Hercules, Inc. lOûcc of the resultant slurry was found to filter in 5 minutes. However, X-ray diffraction (XRD) analysis of the filter cake indicated that the layers had collapsed due to removal of the octylamine.
The procedure of Example 2 was repeated but with the i-propyl alcohol being replaced by acetone. lOOcc of the resultant slurry were found to filter in 5 minutes. XRD analysis of the ~ .
1~87%85 filter cake indicated that the octylamine was retained between the silicate layers of the magadiite.
The procedure described in Example 3 was repeated with 25cc of methylethylketone instead of acetone. lOOcc of the resultant slurry were found to filter in 5 minutes. XRD analysis of the filter cake indicated that the octylamine was retained between the silicate layers of the magadiite.
METHOD FOR FLOCCULATING SUSPENSIONS CONTAINING
-SWELLED LAYERED CHALCOGENIDE
The present invention relates to a method for flocculating aqueous suspensions containing a swelled layered chalcogenide material.
Many layered materials are known which have three-dimensional structures which exhibit their strongest chemical bonding in only two dimensions. In such materials, the stronger chemical bonds are formed in two-dimensional planes and a three-dimensional solid is formed by stacking such planes on top of each other. However, the interactions between the planes are weaker than the chemical bonds holding an individual plane together. The weaker bonds generally arise from interlayer attractions such as Van der Waals forces, electrostatic interactions, and hydrogen bonding.
In those situations where the layered structure has electronically neutral sheets interacting with each other solely through Van der Waals forces, a high degree of lubricity is manifested as the planes slide across each other without encountering the energy barriers that arise with strong interlayer bonding. Graphite is an example of such a material. The silicate layers of a number of clay materials are held together by electrostatic attraction mediated by ions located between the layers. In addition, hydrogen bonding interactions can occur directly between complementary sites on adjacent layers, or can be mediated by interlamellar bridging molecules.
Laminated materials such as clays may be modified to increase their surface area. In particular, the interlamellar spacing can be increased substantially by absorption of various swelling agents such as water, ethylene glycol, amines and ketones, which enter the interlamellar space and push the layers apart.
~ X87X8.r;
However, the interlamellar spaces of such layered materials tend to collapse when the molecules occupying the space are removed, for example, by exposinq the clays to high temperatures. Accordingly, such layered materials having enhanced surface area are not suited for use in chemical processes involving even moderately severe conditions.
Layered metal chalcogenide materials enjoying thermal stability can be prepared by the method described in our European published Patent Application No. 0 205 711. This method comprises:
treating a layered chalcogenide, specifically an oxide, of at least one element having an atomic number of 4, 5, 12 to 15, 20 to 33, 38 to 51, 56 to 83 and greater than 90, inclusive, which contains ion exchange sites having interspathic cations associated therewith, with an organic compound which is a cationic species, e.g., n-alkylammonium or capable of forming a cationic species e.g., n-alkylamine, to effect exchange with said interspathic cations in order to swell the layered material. An electrically neutral compound capable of conversion to an interspathic polymeric oxide, e.g., tetraethylorthosilicate, is thereafter provided between the layers of the swelled, layered chalcogenide. The compound is then converted to the interspathic polymeric oxide to form the layered material.
The present invention relates to a method for filtering the layered chalcogenide which has been swelled by treatment with the above-mentioned organic compound which is either a cationic species or capable of forming a cationic species. The swelled layered material is present in an aqueous slurry or as a suspension and is ordinarily separated by means of filtration and dried before treatment with the electrically neutral compound capable of conversion to the interspathic polymeric oxide or other chalcogenide between the layers of said material. Simple filtration has been found to be time-consuming insofar as the swelled layered material is in a highly dispersed state. Accordingly, there exists a need for a method of flocculating aqueous suspensions comprising swelled layered chalcogenide materials.
- ~
~287Z~3';
F-4278 ~ 3 ~
Many flocculating agents are known, as disclosed in, for example, "Flocculating Agents," Kirk - Othmer Encyclopedia of Chemical Technology, Third Edition Volume 10, pp. 484 to 523.
Synthetic organic materials are of particular interest as flocculants. Such materials include water-soluble polymeric substances with weight average molecular weights ranging from about 103 to greater than 5X105. Where subunits of the polymer possess a positive charge, the polymer is known as a cationic organic polymeric flocculant.
These cationic polymers include polyammonium compounds such as poly(alkylene polyamines) and poly(hydroxyalkylene polyamines) which are step-growth polymerization products of polyfunctional amines and alkyl dihalides or bifunctional alkyl epoxides and alkyl epoxide derivatives. Polyamine quaternaries, another cationic polymer group are prepared by quaternization of poly(alkylene polyamines) and poly(hydroxyalkylene polyamines) with alkyl halides or sulfates or by step~growth polymerization from dialkylamines, tetraalkyl amines, or derivatives thereof, with suitable bifunctional alkylating agents, and with or without small amounts of polyfunctional primary amines. Vinyl conversion products such as cationic carbamoyl polymers are also useful as cationic flocculation agents.
The present invention relates to a method for flocculating an aqueous suspension comprising 1) a layered chalcogenide material having ion exchange sites and swelled with an intercalated hydrophobic swelling agent and 2) nonintercalated, excess hydrophobic swelling agent, which method comprises a) contacting said suspension with a ketone, water, and a cationic organic polymeric flocculant; b) maintaining the resulting mixture at a sufficiently alkaline pH to prevent exchange of said intercalated hydrophobic swelling agent; and c) separating the swelled layered chalcogenide material from the aqueous mixture, whereby said layered chalcogenide material remains swelled after the separating step.
--1~8728.S
F-4278 ~ 4 ~
It is found that the presence of a small amount of ketone solvent during flocculation with a cation:ic polymer at a controlled pH results in a dramatic improvement in filtration rates. In addition, such treatment does not destroy the integrity of the intercalated material which can therefore be treated with a hydrolyzable pillaring agent to form a thermally stable pillared product.
The floc mixture conveniently comprises 3 to lO wt.~ ketone based upon total solution and about l to 3 wt.~ of cationic organic polymer based upon actual solids in the slurry. The slurry is diluted to about 2 to 6 times the initial slurry volume using the ketone/water solution. The cationic organic polymeric flocculant is preferably added in an amount between l and 5 parts, preferably l to 3 parts by weight, compared to the weight of suspension solid.
The layered chalcogenide material employed in the present invention can be a layered oxide, sulfide, selenide or telluride, although preferably is a layered oxide material. Suitable layered oxide materials include layered oxides of Group IVA metals such as titanium, zirconium and hafnium, e.g., layered titanates such as Na2Ti307 as disclosed in U.S. Patents 4,6û0,503, and 2,496,993. Other layered chalcogenide materials in which the present invention may be used to facilitate intercalation include KTiTaO5 and Na4Mnl40279H20, as well as layered oxides of alumina and silicon such as clays, e.g. bentonite. In particular, the present invention can facilitate intercalation of layered silicates known as high silica alkali silicates whose layers lack octahedral sheets. These silicates can be prepared hydrothermally from an aqueous reaction mixture containing silica and caustic at relatively moderate temperatures and pressures, and may contain tetracoordinate framework atoms other than Si. Included among these materials are magadiite, natrosilite, kenyaite, makatite and kanemite, preferably their acid-exchanged forms.
The hydrophobic swelling agent employed in the present invention comprises a source of organic cations, such as 1287Z8.'-, F-4278 ~ 5 organoammonium cation, in order to effect an exchange of the interspathic cations resulting in the layers of the starting material being propped apart. In particular, protonated alkylamines are preferred, such as n-dodecylammonium, n-octylammonium, n-heptylammonium, n-hexylammonium and n-propylammonium cations. The source of organic cation in those instances where the interspathic cations include hydrogen or hydronium ions rnay include a neutral compound such as organic amine which is converted to a cationic analogue during the swelling or "propping" treatment. Among these materials are C3 to Clû, preferably C6 to C8 alkylamines, preferably n-alkylamines, or C3 to ClO, preferably C6 to C8 alkanols, preferably n-alkanols.
Any ketone may be used in the flocculation step which is capable of solubilizing the hydrophobic swelling agent employed.
Such ketones include C3to ClO ketones, preferably C3 to C5 ketones, e.g. methylethylketone or acetone. Preferably the ketone is added to the suspension prior to addition of the cationic organic polymeric flocculant.
The cationic organic polymeric flocculant employed preferably has a molecular weight of 5 x 105 to l x 107, more preferably l x 106 to 5 x lO6. Such materials are synthetic polyelectrolytes carrying a positive charge that serve to destabilize an emulsion by a combination of a) bridging and b) charge neutralization.
pH conditions employed in the present invention are generally sufficiently alkaline so as to prevent the formation of protons which will undesirably exchange with the protonated amine or alkanol swelling agent, resulting in collapse of the layered chalcogenide structure. Generally, the pH should be greater than 5, preferably from 9 to ll.
The invention is further described by the following Examples.
1~8728~
EXAMPLE 1 (COMPARATIVE) Twenty grams of natural magad;ite were sized to pass through a 25 mesh size screen and added to 100 ml of H20. The mixture was adjusted to a pH of about 2 and held there by addition of 0.1 N HCl within a 24 hour period. A total of 435 ml of O.lN HCl was used. The sample was filtered, water-washed and dried. The x-ray pattern of the sample showed a peak at 7.8 (2 theta) indicating an 11.3A d-spacing corresponding to the structure being in a collapsed state. The calcined sample (3 hours at 538C in air) had the same d-spacing. The adsorption properties were 27 m2/g surface area, 0.8% H20, 1.2% CyC6 and 2.0% n-C6. 5009 of an aqueous slurry containing 6759 of the acid-exchanged magadiite were treated with 16009 of n-octylamine to prop open or swell the layers. In order to recover the swelled product, lOOcc of the above slurry was subjected to vacuum filtration, a process which required more than 16 hours to recover 14gms of the swelled product.
EXAMPLE 2 (COMPARATIVE) lOOcc of the slurry described in Example 1 were mixed with 25cc of i-propyl alcohol, 375cc of water and lgm of Hercofloc~3 834, at a pH of lû. Hercofloc~ 834 is a cationic polymer which is composed of an acrylamide based copolymer with a typical viscosity range of 50,000 to 100,000 cps, sold by Hercules, Inc. lOûcc of the resultant slurry was found to filter in 5 minutes. However, X-ray diffraction (XRD) analysis of the filter cake indicated that the layers had collapsed due to removal of the octylamine.
The procedure of Example 2 was repeated but with the i-propyl alcohol being replaced by acetone. lOOcc of the resultant slurry were found to filter in 5 minutes. XRD analysis of the ~ .
1~87%85 filter cake indicated that the octylamine was retained between the silicate layers of the magadiite.
The procedure described in Example 3 was repeated with 25cc of methylethylketone instead of acetone. lOOcc of the resultant slurry were found to filter in 5 minutes. XRD analysis of the filter cake indicated that the octylamine was retained between the silicate layers of the magadiite.
Claims (9)
1. A method for flocculating an aqueous suspension comprising 1) a solid layered chalcogenide material having ion exchange sites and swelled with an intercalated hydrophobic swelling agent and 2) nonintercalated, excess hydrophobic swelling agent;
which method comprises a) contacting the suspension with ketone, water, and a cationic organic polymeric flocculant; b) maintaining the resulting mixture at a sufficiently alkaline pH to prevent exchange of the intercalated hydrophobic swelling agent; and c) separating the swelled layered chalcogenide material from the aqueous mixture; whereby the layered chalcogenide material remains swelled after the separating.
which method comprises a) contacting the suspension with ketone, water, and a cationic organic polymeric flocculant; b) maintaining the resulting mixture at a sufficiently alkaline pH to prevent exchange of the intercalated hydrophobic swelling agent; and c) separating the swelled layered chalcogenide material from the aqueous mixture; whereby the layered chalcogenide material remains swelled after the separating.
2. The method of claim 1 wherein the layered chalcogenide comprises a layered oxide.
3. The method of claim 2 wherein the layered oxide material is a layered titanate or a layered silicate.
4. The method of claim 1,2 or 3 wherein the ketone is a C3 to C10 ketone.
5. The method of claim 1,2 or 3 wherein the cationic organic polymeric flocculant has a molecular weight of 5 x 105 to 1 x 107.
6. The method of claim 1,2 or 3 wherein the suspension is contacted with the ketone prior to contact with the cationic organic polymeric flocculant.
7. The method of claim 1,2 or 3 wherein the pH is from 9 to 11.
8. The method of claim 1,2 or 3 wherein the mixture comprises ketone and water in proportions of 1 to 20 parts by weight of ketone and 99 to 80 parts by weight of water, and the cationic organic polymeric flocculant is added in proportion to the suspension solid at 1 to 5 parts by weight compared to the solids weight.
9. The method of claim 1,2 or 3 wherein the mixture comprises ketone and water in proportions of 3 to 10 parts by weight of ketone and 97 to 90 parts by weight of water, and the cationic organic polymeric flocculant is added in proportion to the suspension solid at 1 to 3 parts by weight compared to the solids weight.
1903h/0027h
1903h/0027h
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/044,184 US4728439A (en) | 1987-04-30 | 1987-04-30 | Method for flocculating suspensions containing swelled layered chalcogenide |
| US044,184 | 1987-04-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1287285C true CA1287285C (en) | 1991-08-06 |
Family
ID=21930956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000548133A Expired - Lifetime CA1287285C (en) | 1987-04-30 | 1987-09-29 | Method for flocculating suspensions containing swelled layered chalcogenide |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4728439A (en) |
| EP (1) | EP0288638B1 (en) |
| JP (1) | JPS63274490A (en) |
| CA (1) | CA1287285C (en) |
| DE (1) | DE3766824D1 (en) |
| DK (1) | DK516087A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5128303A (en) * | 1986-06-27 | 1992-07-07 | Mobil Oil Corporation | Layered metal oxides containing interlayer oxides and their synthesis |
| US4956517A (en) * | 1989-12-29 | 1990-09-11 | Mobil Oil Corporation | Dehydrogenation process utilizing a pillared layered silicate plus a base metal or noble metal |
| US5008481A (en) * | 1989-12-29 | 1991-04-16 | Mobil Oil Corporation | Aromatization process utilizing a pillared layered silicate plus a base metal or noble metal |
| US5980749A (en) * | 1998-06-02 | 1999-11-09 | Light Year Technologies (Usa) Inc. | Inclusion methods for purifying a solvent |
| US6339121B1 (en) * | 2000-03-14 | 2002-01-15 | The Research Foundation At State University Of New York | Compatibilizer for immiscible polymer blends |
| US7521499B2 (en) * | 2001-09-28 | 2009-04-21 | Research Foundation Of State University Of New York | Flame retardant and UV Absorptive polymethylmethacrylate nanocomposites |
| US20090306261A1 (en) * | 2004-07-21 | 2009-12-10 | Research Foundation Of State University Of New York | Compatibilizing Polymer Blends by Using Organoclay |
| WO2007061887A2 (en) * | 2005-11-18 | 2007-05-31 | Research Foundation Of State University Of New York | Partially compatibilized pvc composites |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046684A (en) * | 1974-06-21 | 1977-09-06 | Ebara Infilco Kabushiki Kaisha | Process for the treatment of a colloidal suspension |
| US4176090A (en) * | 1975-11-18 | 1979-11-27 | W. R. Grace & Co. | Pillared interlayered clay materials useful as catalysts and sorbents |
| US4009103A (en) * | 1976-07-12 | 1977-02-22 | Tee-Pak, Inc. | Method for improving the filterability of aluminum salts precipitated from aqueous solutions |
| US4288422A (en) * | 1979-02-23 | 1981-09-08 | Exxon Research & Engineering Co. | Method of preparing chalcogenides of group VIII by low temperature precipitation from monaqueous solution, the products produced by said method and their use as catalysts |
| US4414137A (en) * | 1982-03-09 | 1983-11-08 | Union Oil Company Of California | Catalytically active amorphous silica |
| US4569768A (en) * | 1983-10-07 | 1986-02-11 | The Dow Chemical Company | Flocculation of suspended solids from aqueous media |
| GB8405531D0 (en) * | 1984-03-02 | 1984-04-04 | Nadeau P H | Randomly interstratified clays |
| NZ214538A (en) * | 1984-12-28 | 1989-04-26 | Mobil Oil Corp | Layered product having layers separated by polymeric pillars |
-
1987
- 1987-04-30 US US07/044,184 patent/US4728439A/en not_active Expired - Fee Related
- 1987-09-29 CA CA000548133A patent/CA1287285C/en not_active Expired - Lifetime
- 1987-10-01 DE DE8787308732T patent/DE3766824D1/en not_active Expired - Fee Related
- 1987-10-01 DK DK516087A patent/DK516087A/en not_active Application Discontinuation
- 1987-10-01 EP EP87308732A patent/EP0288638B1/en not_active Expired
- 1987-10-06 JP JP62253455A patent/JPS63274490A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3766824D1 (en) | 1991-01-31 |
| EP0288638B1 (en) | 1990-12-19 |
| DK516087A (en) | 1988-10-31 |
| JPS63274490A (en) | 1988-11-11 |
| US4728439A (en) | 1988-03-01 |
| DK516087D0 (en) | 1987-10-01 |
| EP0288638A1 (en) | 1988-11-02 |
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