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WO1996004981A1 - Procede de separation de materiaux - Google Patents

Procede de separation de materiaux Download PDF

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Publication number
WO1996004981A1
WO1996004981A1 PCT/US1995/009679 US9509679W WO9604981A1 WO 1996004981 A1 WO1996004981 A1 WO 1996004981A1 US 9509679 W US9509679 W US 9509679W WO 9604981 A1 WO9604981 A1 WO 9604981A1
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WO
WIPO (PCT)
Prior art keywords
naphthalenesulfonate
condensate
based carbonyl
organic phase
mixture
Prior art date
Application number
PCT/US1995/009679
Other languages
English (en)
Inventor
William G. Kozak
Dharmesh Chovatia
George A. Smith
Michael J. Virnig
Phillip L. Mattison
Keith E. Weerts
Original Assignee
Henkel Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US08/287,014 external-priority patent/US5501796A/en
Priority claimed from US08/395,774 external-priority patent/US5575918A/en
Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to AU32731/95A priority Critical patent/AU3273195A/en
Publication of WO1996004981A1 publication Critical patent/WO1996004981A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • 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
    • C02F1/26—Treatment of water, waste water, or sewage by extraction

Definitions

  • This invention relates to a process for separating naphthalenesulfonate-based carbonyl condensates from water.
  • U.S. Patent No. 5,015,456 discloses a continuous process for the removal of at least one of nitrate and organic contaminants from an aqueous effluent.
  • the process comprises subjecting said effluent to extractive liquid ion-exchange with a long-chain alkylamine dissolved in an organic solvent and present in the sulfate salt form, and reextracting the loaded organic phase with a base, the treated effluent being recycled for reuse.
  • the amine extractant should be available in the sulfate form, as is also required for the removal of nitrate.
  • Chemical Abstracts 97:12615 and 104: 131988 disclose the extraction and exchange of alkyl sulfates and aryl sulfonates by solutions of trinonyloctadecylammonium chloride in mixtures of toluene and other co- solvents.
  • Chemical Abstracts 92:29200 discloses the selective separation of benzenesulfonic acid from sulfuric acid by extraction with a solution of trioctylamine in xylene.
  • Chemical Abstracts 100:162715 discloses the separation of aromatic sulfonic acids from sulfuric acid using solutions of primary, secondary and tertiary amines in various solvents.
  • Chemical Abstracts 105:45188 discloses the use of a xylene solution of trioctylamine to separate the following from sulfuric acid: 3-nitrobenzenesulfonic acid, benzene-1 ,3-disulfonic acid, 1 -nitronaphthalene-3,6,8-trisulfonic acid, and mixed naphtholsulfonic acids. In none of these cases were the species extracted polymeric molecules.
  • This invention relates to a process for the separation of naphthalenesulfonate-based carbonyl condensates from water, said process comprising: contacting a mixture comprised of water and a naphthalenesulfonate- based carbonyl condensate (preferably a material selected from the group consisting of formaldehyde condensates of naphthalenesulfonic acids, formaldehyde condensates of lower-alkyl substituted naphthalenesulfonic acids, and mixtures of two or more of such materials) with a liquid organic phase comprised of a cationic lipophilic amine to form an aqueous phase depleted with respect to said mixture of naphthalenesulfonate-based carbonyl condensate and an organic phase enriched in naphthalenesulfonate- based carbonyl condensate, and separating said aqueous phase depleted with respect to said mixture of
  • the process preferably further comprises stripping said liquid organic phase of at least a portion of the naphthalenesulfonate-based carbonyl condensate, i.e. depleting said liquid organic phase of naphthalenesulfonate- based carbonyl condensate, and recycling at least a portion of the depleted liquid organic phase to contact additional mixture of water and a naphthalenesulfonate-based carbonyl condensate.
  • This invention also relates to a process for the separation of naphthalenesulfonate-based carbonyl condensates from water, said process comprising: contacting a mixture comprised of water and a naphthalenesulfonate- based carbonyl condensate with a liquid organic phase comprised of a lipophilic non-quaternary amine and a water-immiscible diluent to form an aqueous phase depleted with respect to said mixture of naphthalenesulfonate-based carbonyl condensate and a liquid organic phase enriched in naphthalenesulfonate-based carbonyl condensate, separating said aqueous phase depleted with respect to said mixture of naphthalenesulfonate-based carbonyl condensate and said liquid organic phase enriched with respect to naphthalenesulfonate-based carbonyl condensate, wherein said aqueous phase de
  • the process preferably further comprises treatment of at least a portion of said aqueous solution enriched in naphthalenesulfonate-based carbonyl condensate to separate inorganic salts from polymeric molecules of naphthalenesulfonate-based carbonyl condensate.
  • the first step in the process of this invention involves contacting a mixture comprised of water and a naphthalenesulfonate-based carbonyl condensate with a liquid organic phase comprised of a cationic lipophilic amine to form an aqueous phase depleted with respect to said mixture of naphthalenesulfonate-based carbonyl condensate and a liquid organic phase enriched in naphthalenesulfonate-based carbonyl condensate.
  • the naphthalenesulfonate-based carbonyl condensate is preferably a material selected from the group consisting of formaldehyde condensates of naphthalenesulfonic acids, formaldehyde condensates of lower-alkyl substituted naphthalenesulfonic acids, and mixtures of two or more of such materials.
  • Other examples of naphthalene-based carbonyl condensates include the condensation products of acetone with naphthalenesulfonic acid.
  • the naphthalenesulfonate-based material will typically be a mixture of chemical species.
  • the naphthalene will typically be derived from coal tar or a petroleum base that will contain naphthalene and one or more lower-alkyl naphthalenes.
  • sulfonation of the naphthalene base will typically produce a mixture containing some di-sulfonated naphthalenes and/or some un-sulfonated naphthalenes.
  • the sulfonation of naphthalene is described by E. A. Knaggs, "Sulfonation and Sulfation", Encyclopedia of Chemical Technology, vol. 2, p.
  • Naphthaleneformaldehyde sulfonic acid is a mixture of condensation products of naphthalenesulfonic acid and formaldehyde, such condensation products differing, for example, in the degree of polymerization. It can be chromatographed by size exclusion chromatography through a column containing pore sizes which selectively separate molecular volumes according to size, thus allowing one to obtain a measure of the degree of polymerization.
  • the solvent chosen for the acid in chromatography should minimize solute-packing interaction and solute-solute interaction.
  • the chromatogram gives a true molecular volume profile when the eluents are displayed on a detector-strip chart recorder display. For example, if the chromatogram for a sample of the sulfonic acid is the same as that for the sodium naphthaleneformaldehyde sulfonate in U.S. Pat. No. 3,954,491 (Adrian et al, issued May 4, 1976), the two anionic materials are identical.
  • the anionic materials from the acid have the same profile as the anionic materials from the sodium naphthaleneformaldehyde sulfonate having lowest elution volumes of from above 61 to about 70% of the total elution volume and equivalent elution volumes of from about 61 to about 70% of the total elution volume.
  • the teachings in U.S. Pat. No. 3,954,491 relating to chromatography are incorporated by reference herein.
  • the condensates will generally be water soluble.
  • the naphthalenesulfonic acid and lower alkyl substituted naphthalenesulfonic acids used as starting materials for the condensation will typically have a molecular weight below about 350.
  • Examples of lower alkyl naphthalenesulfonic acids which will be useful herein are those wherein the total of the carbon atoms in the alkyl groups will be less than 16.
  • Such examples include methyl naphthalenes, ethyl naphthalenes, iso-propyl naphthalenes, di-isoprop ⁇ l naphthalenes, butyl naphthalenes.
  • Typical condensates will have a number average molecular weight of from about
  • naphthalene-based condensates are the formaldehyde condensates of naphthalenesulfonic acids and formaldehyde condensates of lower-alkyl substituted naphthalenesulfonic acids.
  • Sulfonated naphthalenes can be employed in the manufacture of naphthalenesulfonate formaldehyde condensates.
  • the naphthalene base can be sulfonated during the condensation with formaldehyde.
  • Such condensation produces a product that can be considered naphthaleneformaldehyde sulfonic acid and is also known as the naphthalenesulfonic acid-formaldehyde condensates, formalin condensates of beta-naphthalenesulfonic acid, condensation products of naphthalenesulfonic acid with formaldehyde.
  • Naphthaleneformaldehyde sulfonic acid may be prepared by reacting a mixture of naphthalene, formaldehyde and sulfuric acid or oleum. It may be prepared by the processes described in U.S. Pat. No. 2, 141 ,569 (Tucker et al, issued Dec. 27, 1938), U.S. Pat. No. 3,193,575 (Nebel et al, issued July 6, 1965), and
  • the mixture of water and naphthalenesulfonate-based material will typically contain only a minor amount of naphthalene-based material. Such minor amounts will generally range from about 10 parts per million to about 5% by weight and more typically from about 0.05% to about 1.0% by weight. Typically, the mixture will also be comprised of only minor amounts of other dissolved or dispersed species. Thus, the mixture will typically be at least about 90%, more typically at least about 95%, and most typically at least about 99.0% by weight water.
  • the first step of the process is to contact the mixture of water and naphthalenesulfonate-based carbonyl condensate with a liquid organic phase comprised of a cationic lipophilic amine.
  • the liquid organic phase comprised of a cationic lipophilic amine will be substantially immiscible with the mixture of water and naphthalenesulfonate-based carbonyl condensate.
  • substantially immiscible is meant that the liquid organic phase, when admixed with the mixture of water and naphthalenesulfonate-based carbonyl condensate to be extracted, will coalesce into a liquid phase that is physically separable from the water of the mixture. This process is, in essence, a liquid-liquid extraction.
  • the principles and mechanics of liquid-liquid extraction are disclosed in T. C. Lo and M. H. I. Baird,
  • the substantially immiscible liquid organic phase is preferably truly immiscible or only very sparingly soluble in the mixture to eliminate or minimize the need to remove residual liquid organic phase from the water of the mixture.
  • the cationic lipophilic amines may be quaternary amines as well as other amines that have a sufficient number of aliphatic or aromatic carbon atoms to render the amine lipophilic, i.e. essentially insoluble in water, even when in cationic form.
  • Preferred amines are non-quaternary amines because it has been found that quarternary amines exihibit such a high affinity for the condensates of naphthalenesulfonates that it is impractical to separate the quarternary amines from the condensates of naphthalenesulfonates after the extraction. Thus, the quarternary amines cannot be re-used to extract new aliquots of aqueous phase containing condensates of naphthalenesulfonates.
  • the non-quaternary amines used in this invention are dissolved in a diluent to provide the liquid organic phase used in the liquid-liquid extraction process.
  • the diluent is a water-immiscible liquid solvent capable of dissolving the non-quaternary amine and the associated ion pair complex of cationic amine and naphthalenesulfonate-based carbonyl condensate.
  • the choice of diluent will depend on a number of factors, including the nature of the contacting equipment being used, the characteristics of the non- quaternary amine, and the presence or absence of modifiers. Examples of diluents include toluene, xylene, octane, mineral spirits, and kerosenes.
  • Kerosenes are preferred, several types of which are available. Examples of commercially available kerosenes include Chevron Ion Exchange Solvent (available form Standard Oil of California - flash point 195°F.), Escaid 100 and 1 10 (available from Exxon-Europe - flash point 180°F.), Exxon Aromatic 150 (an aromatic kerosene available from Exxon-USA - flash point 160°F.),
  • the lipophilic non-quaternary amines are primary, secondary or tertiary amines that have a sufficient number of aliphatic or aromatic carbon atoms to render the amine lipophilic, i.e. essentially insoluble in water, even when in cationic form.
  • the amine will typically have at least 12 carbon atoms, preferably at least 18 carbon atoms.
  • Preferred amines are tri-alkyl tertiary amines wherein the total number of carbon atoms in the alkyl groups is at least 22, preferably at least 24 carbon atoms, and each of the alkyl groups has at least four carbon atoms.
  • lipophilic tertiary amines include tri-isooctylamine, tridodecylamine, and tri-(C8-C10alkyl)amine (the latter being a compound where the alkyl groups are derived from a source of fatty alkyl groups wherein the eight carbon and ten carbon alkyl groups predominate).
  • At least a portion, and preferably substantially all, of the lipophilic amine will be in the cationic form during the contacting and separating steps.
  • the extent to which tertiary amines will be present as the protonated amine will depend upon the precise basicity of the amine and the pH of the aqueous mixture of water and naphthalenesulfonate-based carbonyl condensate.
  • the pH of the aqueous phase at least just prior to the separating step, should be on the acid side of neutral, preferably below about pH 3.
  • the liquid organic phase is provided to the contacting step with the amine in its neutral, unprotonated form, and the aqueous feed mixture of water and naphthalenesulfonate-based carbonyl condensate is adjusted with a mineral acid to contain a ratio of acid equivalents of mineral acid to amine equivalents of lipophilic amine in the liquid organic phase of at least about 1.
  • the ratio is between about 1 and about 3, and more preferably between about 1 and about 1.5.
  • the amine when the liquid organic phase is contacted with the aqueous feed mixture of water and naphthalenesulfonate- based carbonyl condensate, the amine is able to extract an equivalent of acid and be converted substantially to its cationic form.
  • the organic phase is pre-acidified before contacting the mixture of water and naphthalenesulfonate-based carbonyl condensate. This is carried out by contacting the liquid organic phase with an aqueous solution of a mineral acid, wherein the ratio of acid equivalents of the aqueous solution of mineral acid to the amine equivalents of the liquid organic phase is at least 1 . Preferably the ratio is between 1 and 10, and more preferably between 2 and 5.
  • the preferred mineral acid is sulfuric acid, hydrochloric acid or nitric acid, with sulfuric acid being most preferred.
  • the lipophilic non-quaternary amine in the liquid organic phase will have a sufficient affinity for the naphthalenesulfonate-based carbonyl condensate to cause the naphthalenesulfonate-based carbonyl condensate to be extracted into the fluid extractant by anion exchange during the contacting step.
  • the liquid organic phase and the aqueous mixture are placed in extractive contact (i.e., greater than minimal contact is induced between the liquid organic phase and the mixture of water and naphthalenesulfonate-based carbonyl condensate).
  • Such contact generally involves mixing of the liquid organic phase and the aqueous feed mixture to generate increased interfacial surface area between organic and aqueous phases.
  • the conditions under which the aqueous feed mixture of water and naphthalenesulfonate-based carbonyl condensate is mixed with the liquid organic phase generally involve ambient or mildly elevated temperature (e.g., 60° C. to 100° C.) and elevated pressure if necessary to contain water or organic vapor.
  • Both the amount of the liquid organic phase and the amount of the lipophilic non-quaternary amine used may vary. It is generally desirable to provide at least an equivalent amount of amine with respect to the naphthalenesulfonate-based carbonyl condensate, and more preferred to have an excess of amine. However, it is not generally desirable to provide a large excess of amine since the excess of amine over naphthalenesulfonate-based carbonyl condensate will extract another anion as counter-ion, such as the anion of the mineral acid added. Then, when the liquid organic phase is stripped with an alkaline solution, the other counter- ion also transfers to the aqueous strip solution and forms a salt.
  • the liquid organic phase will contain an amount of the lipophilic non- quaternary amine such that the ratio of amine equivalents to sulfonate equivalents of the naphthalenesulfonate-based carbonyl condensate in the mixture is from about 0.5:1 to about 5:1 , preferably from about 1 :1 to about
  • the weight ratio of aqueous phase (provided by the mixture of water and naphthalenesulfonate-based carbonyl condensate) to liquid organic phase may also vary broadly. The precise ratio chosen will depend, at least in part, on the apparatus and operating regime thereof that is chosen for the contacting and separation. Typically, the ratio will be from about 5:1 to about 1 :5, and more typically from about 2:1 to about 1 :2.
  • the aqueous phase and liquid organic phases are separated to form an aqueous phase depleted in naphthalenesulfonate-based carbonyl condensate and an organic phase enriched in naphthalenesulfonate-based carbonyl condensate.
  • the phases will separate, e.g., coalesce, into separate phases during the quiescent period following the cessation of mixing of the two phases.
  • One of the phases, typically the liquid organic phase will typically have a lower density than the other phase, typically the aqueous phase, which will allow one to physically separate the two phases, e.g., by decanting off the liquid organic phase.
  • the method of contacting and separating can be operated in a batch or a continuous mode.
  • the liquid organic phase with a cationic lipophilic amine can be divided into a plurality of aliquots for multiple batch extractions of the mixture of water and naphthalenesulfonate-based carbonyl condensate (i.e., a multistage extraction) or it can be contacted with the mixture in a continuous manner (e.g., co-current, cross-current or counter- current).
  • Apparatus conventionally employed in liquid-liquid extractions include mixer-settlers, stirred tanks, un-agitated columns, pulsed columns, rotary agitated columns, reciprocating plate columns, and centrifugal extractors.
  • the apparatus employed to effect the method of contacting and separating will, of course, be appropriate for the precise method of contacting and separating that is chosen.
  • the apparatus is operated in a batch mode. In batch mode, the liquid organic phase and the mixture of water and naphthalenesulfonate- based carbonyl condensate are fed to a vessel and the contents are mixed.
  • aqueous and liquid organic phases are then separated by decanting liquid off the top or drawing liquid from the bottom.
  • the liquid organic phase is removed from the vessel and a second extraction of the same aqueous phase is effected by adding fresh liquid organic phase, and then the sequence of mixing and settling is repeated.
  • the aqueous phase is removed from the vessel and is replaced by a second portion of mixture of water and naphthalenesulfonate-based carbonyl condensate, and the sequence of mixing and settling is repeated.
  • the apparatus is operated in a continuous mode.
  • a mixture of water and naphthalenesulfonate-based carbonyl condensate is fed into a first feed port (for a heavier liquid, near the top of a vertical, stirred, extractor column).
  • the mixture falls through the column while a liquid organic phase containing a lipophilic non-quaternary amine is fed to a second feed port (for a lighter liquid, near the base of the column).
  • the liquid organic phase rises through the stirred column, i.e., countercurrent to the flow of the mixture of water and naphthalenesulfonate-based carbonyl condensate.
  • the aqueous phase is withdrawn from the column through a bottom exit port below this zone of separation.
  • the liquid organic phase is withdrawn from the column through a top exit port.
  • a more preferred embodiment of continuous operation of this process employs mixer-settlers, especially in counter-current mode.
  • both liquid organic phase and the aqueous phase mixture of water and naphthalenesulfonate-based carbonyl condensate are fed continuously to a stirred mixing vessel in which the phases are mixed to form an emulsion with high interfacial surface area.
  • the outlet of the mixer continuously flows to a settling tank where the liquid organic phase, now enriched in naphthalenesulfonate-based carbonyl condensate, separates from the depleted aqueous phase.
  • the separated phases continuously overflow through an arrangement of weirs, and are advanced to the next step of the process.
  • the extraction process of contacting and separating is repeated through two or more mixer-settler stages, in order to more completely extract the naphthalenesulfonate-based carbonyl condensate.
  • aqueous phase mixture of water and naphthalenesulfonate-based carbonyl condensate will flow through an initial mixer-settler stage ("E1 "), subsequently through a second stage ("E2"), and then through a final mixer-settler stage ("E3").
  • E1 initial mixer-settler stage
  • E2 second stage
  • E3 final mixer-settler stage
  • the liquid organic phase will, in turn, initially contact the aqueous feed solution in E3, encounter a subsequent contact in E2 and a final contact in E1.
  • the naphthalenesulfonate- based carbonyl condensate is separated from the enriched liquid organic phase by contacting the enriched liquid organic phase with an aqueous stripping solution to form a stripped organic phase and an aqueous stripping solution enriched in naphthalenesulfonate-based carbonyl condensate.
  • the stripping solution should have sufficient alkalinity so that at least a portion of the cationic lipophilic amine in the organic phase is converted to the neutral or free base form.
  • the stripping solution will be an aqueous solution which contains an alkaline compound in stoichiometric excess to the cationic lipophilic amine in the liquid organic phase.
  • the ratio of alkali equivalents of the alkaline compound to the amine equivalents of cationic amine will preferably be between 1 :1 and 100:1 , more preferably between 1.5: 1 and 50: 1 , and still more preferably between 2: 1 and 10: 1 .
  • the pH at which the cationic lipophilic amine is converted to the neutral or free base form is pH 5 or above. Consequently, it is preferred that the amount of alkaline compound provided in the stripping solution be sufficient to provide a pH of at least 5 after contacting the enriched liquid organic phase. More preferably the pH of this aqueous solution enriched in naphthalenesulfonate-based carbonyl condensate will be at least about 7, and still more preferably at least about 9.
  • Preferred alkaline compounds are sodium hydroxide, potassium hydroxide, ammonium hydroxide and ammonia, with the most preferred being sodium hydroxide.
  • the stripped organic phase can then be recycled to the extraction contacting step. This permits the organic phase to be reused indefinitely.
  • at least a portion of the stripping solution enriched in naphthalenesulfonate-based carbonyl condensate is also recycled to contact a further portion of enriched liquid organic phase. This permits the further enrichment of the stripping solution in naphthalenesulfonate-based carbonyl condensate.
  • the process is capable of building high concentrations of naphthalenesulfonate- based carbonyl condensate, effectively transferring it from a relatively large volume of dilute effluent to a relatively small volume of concentrated strip solution.
  • a major portion of the stripping solution enriched in naphthalenesulfonate-based carbonyl condensate is recycled to contact a further portion of enriched liquid organic phase, and a minor portion of the strip solution is removed from the strip stage as a concentrate.
  • the addition of alkaline compound may be controlled by monitoring the pH of the recycling stripping solution.
  • the pH is maintained between about 8 and about 14, more preferably between about 10 and about 13.5, and still more preferably between 12 and 13.
  • the alkaline compound is preferably added as an alkaline solution to the last stage of stripping, i.e., the stage from which stripped organic exits.
  • Strip solution is recycled within each stage, and is advanced progressively from the last stage to the first stage, i.e., the stage from which the aqueous strip solution exits.
  • the rate of advance of strip solution may be controlled by the rate of addition of alkaline solution to the last strip stage, which is in turn controlled by the pH of the strip solution in the first strip stage.
  • alkaline compound may be added to the recycling strip solution at each stage to maintain the desired pH with strip solution being advanced from the last stripping stage to the first stripping stage as the concentration of naphthalenesulfonate-based carbonyl condensate reaches the desired level.
  • An additional embodiment of the invention comprises the further step of treating at least a portion of the aqueous strip solution enriched in naphthalenesulfonate-based carbonyl condensate to separate inorganic salts from the polymeric molecules of naphthalenesulfonate-based carbonyl condensate.
  • this step is accomplished by passing the enriched strip solution through a membrane filtration unit, in which a portion of the water passes through the membrane along with inorganic salts and small molecules, producing a permeate, and the remainder of the water along with the large, polymeric molecules of naphthalenesulfonate-based carbonyl condensate do not pass through the membrane, producing a retentate.
  • a membrane filtration unit in which a portion of the water passes through the membrane along with inorganic salts and small molecules, producing a permeate, and the remainder of the water along with the large, polymeric molecules of naphthalenesulfonate-based carbonyl condensate do not pass through the membrane, producing a retentate.
  • Mineral acid is typically co-extracted along with the polymeric naphthalenesulfonate-based carbonyl condensate in this invention, if completeness of extraction is desired. While the selectivity for extraction of naphthalenesulfonate-based carbonyl condensate over mineral acid is high, some excess of equivalents of amine over equivalents of naphthalenesulfonate- based carbonyl condensate is necessary to drive the extraction more nearly to completion. This excess of amine thus extracts the anion of the mineral acid, which then is carried with the liquid organic phase to stripping.
  • the amine In stripping, the amine is converted to its neutral or nonionic form, and all anions which were associated with the amine transfer to the aqueous stripping phase as a salt.
  • sulfuric acid is used as the mineral acid
  • excess equivalents of amine will extract sulfate anion
  • stripping with sodium hydroxide as the alkaline compound will generate sodium sulfate, along with the sodium salt of naphthalenesulfonate-based carbonyl condensate.
  • a desirable feature of this embodiment of the invention is the ability not only to remove the naphthalenesulfonate-based carbonyl condensate from the aqueous effluent and to recover it as a concentrate, but also to separate the inorganic salts from the polymeric naphthalenesulfonate- based carbonyl condensate, generating a concentrate low in salt and of suitable purity for use as a product having value.
  • the process of this invention preferably further comprises treatment of at least a portion of said aqueous solution enriched in naphthalenesulfonate-based carbonyl condensate to separate inorganic salts from polymeric molecules of naphthalenesulfonate-based carbonyl condensate.
  • This treatment typically comprises exerting pressure on said aqueous solution while said aqueous solution is in contact with a porous membrane; passing a permeate solution containing dissolved inorganic salts, said permeate solution being essentially free of polymeric molecules of naphthalenesulfonate-based carbonyl condensate, through said porous membrane; and collecting polymeric molecules of naphthalenesulfonate- based carbonyl condensate as a retentate.
  • porous membrane any (including “supported layer articles”) having micropores and sufficient structural integrity to withstand the pressure needed to isolate the polymeric molecules of naphthalenesulfonate-based carbonyl condensate from the aqueous mixture over a desired period of time (e.g., from 15 minutes to 24 hours).
  • Nanofiltration processes can be generally described as part of the continuum of separation processes between reverse osmosis filtration and ultrafiltration and which operate at medium to high pressures, generally from about 150 to 600 psi.
  • Reverse osmosis filters separate relatively smaller components having a molecular weight of less than about 500, that is, on a micromolecular scale of less than 1 nm.
  • ultrafiltration is a selective f ractionation type filtration using pressures up to 150 psi to retain and/or purify dissolved or suspended particles of macromolecular species, generally of a specific cut-off from 1000 to 1 ,000,000 in molecular weight. Fluxes in ultrafiltration are an order of magnitude less than in microfiltration.
  • the membranes and membrane configurations typically used for nanofiltration are of the same generally type as are used in reverse osmosis filtration.
  • nanofilters provide the capability to separate low molecular weight organic compounds from monovalent ions such as from various salts like sodium chloride. Further details as to nanofiltration can be found in U.S. Patent No. 5,338,553 (Johnson) which is incorporated herein by reference thereto.
  • an aqueous solution including small dissolved molecules is forced through a porous membrane. Large dissolved molecules that cannot pass through the pores are retained.
  • Components retained by the membrane are collectively referred to as a concentrate or retentate.
  • Components which traverse the membrane are referred to collectively as filtrate or permeate.
  • Diafiltration is a filtration process in which the retentate is further purified or the permeable solids are extracted further by the addition of water to the retentate. This process is analogous to washing of a conventional filter cake.
  • the use of nanofiltration removes salts formed by the neutralization of the alkaline solution and other small molecular species.
  • Nanofiltration is a pressure-driven filtration on a molecular scale.
  • the porous membrane typically has a pore size cutoff ranging from about 0.8 to about 8 nanometers, e.g. 1.0 to 2.0 nanometers.
  • a typical porous membrane is comprised of a porous article having at least one macroscopic passage therethrough (typically a cylindrical article having cylindrical passages) substantially parallel to the axis of symmetry of the cylindrical article.
  • the retentate travels through the macroscopic passage and, thus, the filtration can be characterized as a crossflow filtration.
  • the article may be "porous" itself, the cylinder may act principally as a support (i.e., in a "supported layer article") for a porous layer (or layers with regard to multi- passage articles) which covers the surfaces defined by the passages through the article.
  • the porosity of the article, and any porous layer associated therewith as described above, can be varied as desired, with the pore size of any such layer being smaller than that of the article.
  • such a filter element i.e., cylindrical and porous article
  • slurry is fed into the passages under pressure through a feed manifold that prevents leakage into the housing.
  • the exit of the isolated polymeric molecules of naphthalenesulfonate-based carbonyl condensate from the passages at the other end of the filter element is controlled by an exit manifold which also prevents leakage into the housing where the filtrate or permeate is contained.
  • a further embodiment of this invention provides for contacting of the stripped organic phase with an aqueous solution of a mineral acid prior to recycling for further extraction of naphthalenesulfonate-based carbonyl condensate.
  • This step converts the amine in the liquid organic phase from its neutral form to its cationic form, so that little or no excess acid needs to be supplied in the aqueous feed mixture of water and naphthalenesulfonate- based carbonyl condensate during extraction to maintain the pH below about 3.
  • At least a major portion of the re- acidified aqueous phase is returned to contact a further portion of stripped organic phase.
  • This recycling allows the aqueous to be reused multiple times.
  • a minor or intermittent portion of the re-acidified aqueous can optionally be used as a bleed stream to acidify the aqueous feed mixture of water and naphthalenesulfonate-based carbonyl condensate. This gives a constructive use of the contained acid in the bleed stream, and allows a control for buildup of other components in the aqueous mineral acid solution, such as salts.
  • the separated mixture of water and naphthalenesulfonate-based carbonyl condensate after extraction can be post-treated to remove residual amounts of liquid organic phase using other purification techniques, e.g. treatment with activated carbon or other adsorbents.
  • the extent of the reduction in concentration of naphthalenesulfonate- based carbonyl condensate in the aqueous phase will, of course, depend upon the extent of contact with the liquid organic phase and the precise efficiency of the liquid organic phase under the given contact conditions. Generally, the liquid organic phase will remove at least a significant portion of the naphthalenesulfonate-based carbonyl condensate.
  • the concentration of naphthalenesulfonate- based carbonyl condensate in the water after said contacting and separating are completed will be less than 0.1 %, more typically less than 0.03%, and preferably less than 0.01 %.
  • FIG. 1 is a schematic representation of a preferred embodiment of the process of the invention using mixer-settlers in a continuous mode of operation.
  • an aqueous feed mixture 2 of water and naphthalenesulfonate- based carbonyl condensate is led to a mix tank 1 where the pH is brought to about 3 by addition of mineral acid 48.
  • the acidified aqueous mixture 4 is pumped at a fixed rate to a series of three counter-current extraction mixer- settlers, designated as 3, 5 and 7.
  • Aqueous mixture 4 is mixed in mixer- settler 3 with partially loaded liquid organic phase 16 from mixer-settler 5.
  • the organic-aqueous mixture overflows into the settling compartment of mixer-settler 3, and separates into discrete organic and aqueous phases.
  • Partially extracted aqueous phase 6 flows to the mixer of mixer-settler 5, where it is mixed with organic phase 14 from mixer-settler 7.
  • organic phase 16 flows to the mixer of mixer-settler 3
  • aqueous phase 8 flows to the mixer of mixer-settler 7, where it is mixed with acidified organic phase 12 from mixer-settler 15.
  • organic phase 14 flows to mixer-settler 5, and aqueous phase 10, now depleted of naphthalenesulfonate-based carbonyl condensate, is discharged as treated effluent.
  • a minor second portion 34 of the mixed aqueous stripping stream is diverted as concentrated naphthalenesulfonate-based carbonyl condensate to a pressure filtration unit 19, where an aqueous stream 38 of salt is separated from a product stream 36 of concentrated and purified naphthalenesulfonate-based carbonyl condensate.
  • the organic phase 22 now stripped of naphthalenesulfonate- based carbonyl condensate, flows to an organic phase surge tank 13.
  • the separated aqueous strip phase from mixer-settler 1 1 now enriched in naphthalenesulfonate-based carbonyl condensate, is combined with fresh aqueous alkaline solution 26, and a major first portion 28 of the combined aqueous strip phase is recycled to the mixer of mixer-settler 1 1.
  • a minor second portion 30 flows to be combined with the separated aqueous strip solution from mixer-settler 9.
  • Stripped organic phase 24 from the organic surge tank 13 is pumped at a controlled rate to the mixer of mixer-settler 15, where it is mixed with an aqueous mineral acid solution 40.
  • the organic phase 12 now having its lipophilic amine in the cationic form, flows to the mixer of mixer- settler 7, completing the organic circuit.
  • the separated aqueous phase from mixer-settler 15 flows to an acid wash reservoir 17, where mineral acid 44 is added to maintain a desired level of acidity.
  • a major portion 40 of the aqueous mineral acid solution is pumped to the mixer of mixer-settler 15 to acidify another portion of stripped organic 24, and a minor portion 46 of the aqueous mineral acid solution is pumped to mix tank 1 to assist in acidification of incoming aqueous mixture 2.
  • C8-C10alkyl (available as Alamine 336 from Henkel Corp., Ambler, Pennsylvania) and 75 g of iso-tridecanol (available from Exxon) in Escaid 1 10, a non-aromatic kerosene available from Exxon, and diluting to one liter.
  • Amine concentration in this organic solution is 0.018M.
  • a portion of this organic was pre-acidified by contacting in a separatory funnel with an equal volume of 50 g/L sulfuric acid.
  • Henkel Corp., Ambler, Pennsylvania condensate were first adjusted with sulfuric acid to pH 2.5, and then were contacted with an equal volume of pre-acidified organic by shaking in a separatory funnel. After shaking was stopped, separated aqueous phase was analyzed for naphthalenesulfonate- based carbonyl condensate by conducting a U V scan from 190 nm to 400 nm with a Perkin Elmer spectrophotometer. The absorbance of the aqueous phase at 230 nm was compared with the absorbance at 230 nm of a known sample of 20 ppm of the naphthalenesulfonate-based carbonyl condensate Lomar PL in water.
  • Example 1 The organic solution of Example 1 was loaded to about 4500 ppm Lomar condensate by contacting with Effluent Sample A of Example 1. Loaded organic solution was then stripped by contacting in a separatory funnel with aqueous solutions containing 0.05M sodium hydroxide and either 4.4, 1 1 or 44% Lomar condensate. The resulting organic was separated, filtered, and a portion of the filtered organic was contacted a second time with 0.05M NaOH to determine residual Lomar condensate on the organic phase. The separated aqueous phase was filtered and analyzed by the UV method of Example 1. In each case the Lomar condensate values were 1 1- 1 2 ppm, indicating that the loaded organic was effectively stripped by alkaline solution, even in the presence of high aqueous concentrations of Lomar condensate.
  • Lomar condensate was recovered from effluent Sample B of Example 1 using a laboratory scale circuit of continuous mixer-settlers. Rectangular mixer-settlers had mixer volumes of about 165 mL and settler volumes of about 415 mL. The circuit was configured with three stages of countercurrent extraction, two stages of countercurrent striping, and one stage of acid washing. The stripping mixer-settlers were configured with aqueous recycle to allow build-up of a concentrate of Lomar condensate. The organic phase was formulated to contain 0.01M Alamine 336 and 75 g/L isotridecanol in Escaid 110 kerosene. The aqueous effluent feed was acidified with sulfuric acid to pH 2.5.
  • Aqueous strip solution in the first strip stage (S1) was initially formulated to contain 15 g/L sodium sulfate, and adjusted with sodium hydroxide to pH 13. When returning from the strip stage, this solution was led to a reservoir where additional sodium hydroxide solution was added to maintain pH 13.
  • Aqueous strip solution in the second strip stage (S2) was initially formulated to contain 0.1 M sodium hydroxide and 25 g/L sodium sulfate. Acid wash aqueous solution was formulated to contain 25 g/L sodium sulfate, and sufficient sulfuric acid to reach pH 1 . When returning from the acid wash stage, this aqueous was led to a reservoir where additional sulfuric acid was added to maintain pH 1 .

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Abstract

Procédé de séparation de condensats de carbonyle à base de sulfonate de naphtalène contenus dans de l'eau. Ce procédé consiste à mettre en contact un mélange composé d'eau et d'un condensat de carbonyle à base de sulfonate de naphtalène (de préférence, un matériau sélectionné dans le groupe constitué par des condensats de formaldéhyde d'acide naphtalènesulfonique, par des condensats de formaldéhyde d'acides naphtalènesulfoniques substitués par alkyle inférieur ou par des mélanges de deux ou de plusieurs de ces matériaux) avec une phase liquide organique composée d'une amine cationique lipophile, afin d'obtenir une phase aqueuse appauvrie en condensat de carbonyle à base de sulfonate de naphtalène et une phase liquide organique enrichie en condensat de carbonyle à base de sulfonate de naphtalène. Ce procédé consiste, de plus, à séparer ladite phase aqueuse appauvrie et ladite phase liquide organique enrichie. Celle-ci peut être soumise à une désorption au moyen d'une solution de désorption alcaline, afin de régénérer l'amine cationique lipophile.
PCT/US1995/009679 1994-08-08 1995-08-04 Procede de separation de materiaux WO1996004981A1 (fr)

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AU32731/95A AU3273195A (en) 1994-08-08 1995-08-04 Method for separating materials

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US08/287,014 US5501796A (en) 1994-08-08 1994-08-08 Method for separating materials
US08/287,014 1994-08-08
US08/395,774 US5575918A (en) 1995-02-28 1995-02-28 Method for recovery of polymers
US08/395,774 1995-02-28

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465492A (en) * 1981-08-25 1984-08-14 Ciba-Geigy Corporation Process for the preparation of concentrated aqueous formulations of synthetic anionic dispersants and the use thereof
US5015456A (en) * 1989-05-09 1991-05-14 Bayer Antwerpen Removal of nitrate and/or organic pollutants from effluents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465492A (en) * 1981-08-25 1984-08-14 Ciba-Geigy Corporation Process for the preparation of concentrated aqueous formulations of synthetic anionic dispersants and the use thereof
US5015456A (en) * 1989-05-09 1991-05-14 Bayer Antwerpen Removal of nitrate and/or organic pollutants from effluents

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