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WO2024094892A1 - Inhibition d'incrustation de titanate dans un processus bayer à flux unique - Google Patents

Inhibition d'incrustation de titanate dans un processus bayer à flux unique Download PDF

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Publication number
WO2024094892A1
WO2024094892A1 PCT/EP2023/080854 EP2023080854W WO2024094892A1 WO 2024094892 A1 WO2024094892 A1 WO 2024094892A1 EP 2023080854 W EP2023080854 W EP 2023080854W WO 2024094892 A1 WO2024094892 A1 WO 2024094892A1
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mol
acid
polymer
independently chosen
group
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Inventor
Xia Zhang
Lance Wilson
Jie Lu
Dannon STIGERS
Adam HENKE
Esra ALTAY
Lei Zhang
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Cytec Industries Inc
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Cytec Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/0666—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

Definitions

  • the Bayer process is used for the production of alumina from bauxite.
  • Bauxite is composed primarily of three aluminum minerals: gibbsite (Al(0H)3), boehmite (y- A10(0H)) and diaspore (a-AlO(OH)).
  • gibbsite Al(0H)3
  • boehmite y- A10(0H)
  • diaspore a-AlO(OH)
  • the bauxite ore is heated with caustic to a temperature to dissolve aluminum oxide in an extraction (also referred to as digestion) process where aluminum oxide is converted to soluble sodium aluminate.
  • gibbsite is the most easily digestible, requiring lower digestion temperatures (100-145 °C). Boehmite is more difficult to digest than gibbsite, due to its mineralogy, with a typical digestion temperature range of 225-245 °C. Diaspore is the most difficult ore to digest among all bauxite types. The digestion temperature of diaspore is usually above 250 °C. Lime is usually added to help diaspore digestion, and a longer residence time is also required.
  • Single stream designs are more efficient than double stream designs in terms of energy recovery, water balance, caustic corrosion, and powerhouse cogeneration efficiency.
  • the majority of alumina global production (>70%) is made using single stream designs, and prospective new plants are being designed with single stream flows.
  • the main drawbacks for single stream processes are formation of both silicate scale and titanate scale (particularly in high temperature sections at temperatures greater than 160 °C) on heat exchanger walls, which influences the heat transfer coefficient to the slurry and lowers the digestion efficiency.
  • Such scale forms because in addition to the aluminum ores of interest, bauxite also contains other constituents or gangue minerals, considered “impurities.”
  • the main impurities are minerals of silica, iron and titanium, as well as organic matter.
  • titania When titania is present in the bauxite ore, hard titanate scale forms in the high temperature heat exchangers.
  • Major species of titanate scales formed in single stream alumina refineries include perovskite, kassite, cafetite, and hydroxotitanate.
  • silicate and titanate scale exist in single stream Bayer plants, titanate scale is more problematic due to its difficulty to clean; current methods of cleaning are costly and not HSE friendly. Plants often use hydro-blasting and fire burning to remove titanates. The cleaning cycle of scale in many plants depends on the titanate scale formation due to the faster scaling rate at higher temperatures.
  • embodiments disclosed herein relate to a method of inhibiting titanium-containing scales in an industrial process that includes contacting a reaction medium with a scale inhibitor comprising a polymer comprising pendant phosphonate functional groups.
  • embodiments disclosed herein relate to use of a polymer as a scale inhibitor for titanium-containing scale in an industrial process, the polymer comprising phosphonate functional groups.
  • Embodiments disclosed herein relate to methods of inhibiting scale formation in industrial processes, especially titanate scale in a Bayer process.
  • Methods include contacting an industrial process stream with at least one scale inhibitor.
  • titanate scale tends to accumulate in higher temperature sections of the heat exchangers in alumina refineries.
  • a titanate scale inhibitor which was designed for single stream Bayer processes, may result in improved alumina production and reduced costs.
  • scale inhibitors according to one or more embodiments include at least one polymer having phosphonate (notably -PCh 2 ') functional groups.
  • Use of the scale inhibitor in an industrial process may reduce or even inhibit the formation of scale, particularly titanate scale, in at least the process heat exchangers.
  • the Bayer process may maintain high heat transfer from the heat exchanger to a slurry of Bayer liquor mixed with bauxite.
  • the scale inhibitor may be a polymer comprising phosphonate functional groups.
  • phosphonate functional groups are understood to refer to phosphorous-containing functional groups present on a compound having a tetrahedral phosphorous center with a formula of -PO(OR)2, or ionized to -POs 2 ' .
  • the polymer may be a homopolymer or copolymer comprising a plurality of polymerizable monomers covalently bound to at least one phosphonate functional group.
  • the polymerizable monomers may be a monomer (B) that includes a phosphonate functional group, for example -PO3 2 'functional group, (thereby forming recurring units with such phosphonate group), or the polymer formed from the polymerizable monomer (monomer (A)) may be functionalized to include phosphonate functional groups (for example -PCh 2 ' functional groups).
  • the scale inhibitor may be a copolymer including, in addition to monomer (B) or monomer (A), a polymerizable comonomer.
  • monomer (A) is a polymerizable monomer that upon polymerization results in recurring units that may be functionalized to include phosphonate functional groups (for example -POs 2 ' functional groups).
  • recurring units derived from polymerizable monomers (A) may comply with the formula -(E-N)-, wherein E may be independently chosen from an optionally substituted hydrocarbyl radical having from 2 to 40 carbon atoms.
  • Recurring units derived from polymerizable monomers (A) may be covalently bound to a phosphonate containing group such that the polymer may comprise the formula (I) or (II): wherein each E is independently chosen from an optionally substituted hydrocarbyl radical having from 2 to 40 carbon atoms; each T 1 may be independently chosen from an organic connecting group comprising a substituted or unsubstituted C1-C20 hydrocarbyl group; each T 2 may be independently chosen from a direct bond or an organic connecting group comprising a substituted or unsubstituted C1-C20 hydrocarbyl group; and each R 1 may independently be H, NH4, K, Na, NR 2 4 (where R 2 is methyl), or methyl groups (i.e., dimethyl esters) and n ranges from 2 to 1000.
  • each E is independently chosen from an optionally substituted hydrocarbyl radical having from 2 to 40 carbon atoms
  • each T 1 may be independently chosen from an organic connecting group comprising a substitute
  • hydrocarbyl is a generic term encompassing aliphatic, alicyclic and aromatic groups having an all-carbon backbone and consisting of carbon and hydrogen atoms.
  • one or more of the carbon atoms making up the carbon backbone may be replaced or interrupted by a specified atom or group of atoms, such as by one or more heteroatom of N, O, and/or S.
  • hydrocarbyl groups include alkyl, cycloalkyl, cycloalkenyl, carbocyclic aryl, alkenyl, alkynyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkenylalkyl, and carbocyclic aralkyl, alkaryl, aralkenyl and aralkynyl groups.
  • Such hydrocarbyl groups can also be optionally substituted by one or more substituents as defined herein. Accordingly, the chemical groups or moieties discussed in the specification and claims should be understood to include the substituted or unsubstituted forms.
  • the examples and preferences expressed below also apply to each of the hydrocarbyl substituent groups or hydrocarbyl-containing substituent groups referred to in the various definitions of substituents for compounds of the formulas described herein unless the context indicates otherwise.
  • Suitable examples of polymerizable monomer (A) that may be functionalized to include phosphonate functional groups may include, for example, polyvinylamine, polyallylamine, aziridenes, oxazolines, carboxylic acid monomers such as (meth)acrylic acid, maleic acid, itaconic acid, and acrylamidoglycolic acid; sulfonic acid monomers such as 2-(meth)acrylamido-2-methylpropylsulfonic acid, 3-(meth)acrylamido-2- hydroxypropylsulfonic acid, 3-allyoxy-2-hydroxypropyl-sulfonic acid, vinylsulfonic acid, vinylbenzylsulfonic acid, and allyloxybenzylsulfonic acid; non-ionic monomers such as (meth)acrylamide, t-butylacrylamide, vinyl acetate, and hydroxypoly ethoxy (10) allyl ether; sulfate and phosphate ester analogs of
  • R 3 may be chosen from -H or -CH3.
  • T 1 may be independently chosen from a direct bond or an organic connecting group comprising a substituted or unsubstituted C1-C20 hydrocarbyl group; and each R 1 may independently be H, NH4, K, Na, NR 2 4 (where R 2 is methyl), or methyl groups (i.e., dimethyl esters).
  • Recurring units derived from polymerizable monomers (B) may comply with the following formula (III):
  • Suitable examples of monomer (B) may include aliphatic unsaturated phosphonic acids such as vinyl phosphonic acid, vinylphosphonic acid dimethyl ester, vinyl diphosphonic acid, isopropenylphosphonic acid, vinylidenephosphonic acid, allylphosphonic acid, vinylbenxylphosphonic acid, 2-(meth)acrylamido-2- methylpropylphosphonic acid, 3-(meth)acrylamido-2-hydroxypropylphosphonic acid, 3- allyoxy-2-hydroxypropylphosphonic acid, salts thereof, derivatives thereof, and any mixtures thereof.
  • aliphatic unsaturated phosphonic acids such as vinyl phosphonic acid, vinylphosphonic acid dimethyl ester, vinyl diphosphonic acid, isopropenylphosphonic acid, vinylidenephosphonic acid, allylphosphonic acid, vinylbenxylphosphonic acid, 2-(meth)acrylamido-2- methylpropylphosphonic acid, 3-(meth)acrylamido-2-hydroxypropylphospho
  • suitable comonomers may be any monomer which is polymerizable with monomers (A) and/or monomers (B).
  • Comonomers may comprise an unsaturated group suitable for radical polymerization or may be polymerized by any other method appropriate for polymerization of the desired comonomer.
  • Comonomers may be aliphatic unsaturated carboxylic acids, amides, and derivatives thereof.
  • Suitable examples of comonomers may include hydrophilic comonomers such as acrylic or methacrylic acid, salts thereof, and derivatives thereof; and acrylamide or methacrylamide, and derivatives thereof.
  • suitable comonomers may be acrylic acid, dimethyl acrylamide, N-isoproyl acrylamide, hydroxy ethylacrylate, ethylene oxide, vinyl alcohol, or other suitable hydrophilic monomers, or combinations thereof.
  • Suitable examples of sulfonic acid containing comonomers may include 2- acrylamido-2-m ethyl- 1 -propanesulfonic acid, naphthaleneformaldehyde sulfonate, styrene sulfonate, salts thereof, derivatives thereof, and combinations thereof.
  • Polymers according to the present disclosure may be either homopolymers comprising monomers (A) or monomers (B), or may be copolymers of either monomers (A) or monomers (B) and at least one comonomer, as those that have been described above. Polymers may be either branched or linear.
  • polymers comprising, consisting essentially of, or even consisting of, monomers (A) may comply with Formula (IV), below: where E may be independently chosen from an optionally substituted hydrocarbyl radical having from 2 to 40 carbon atoms; R is independently chosen from H, CH2CH2NH2, or a polyethyleneimine branch point; T 1 is independently chosen from a direct bond or an organic connecting group comprising a substituted or unsubstituted C1-C20 hydrocarbyl group; each R 1 is independently chosen from be H, NH4, K, Na, NR 2 4 (where R 2 is methyl), or methyl groups (i.e., dimethyl esters), and n+m+p ranges from 5 to 2500.
  • E may be independently chosen from an optionally substituted hydrocarbyl radical having from 2 to 40 carbon atoms
  • R is independently chosen from H, CH2CH2NH2, or a polyethyleneimine branch point
  • T 1 is independently chosen from a direct bond or an organic connecting group comprising a substituted or
  • polymers comprising, consisting essentially of, or even consisting of, monomers (B) may comply with Formula (V), below.
  • the polymer is polyvinyl phosphonic acid, a salt thereof, or a derivative thereof, such as polyvinylphosphonic acid dimethyl ester.
  • copolymers comprising monomers (B) may comply with Formula (VI), below.
  • the polymer may be a copolymer of vinylphosphonic acid and at least one unsaturated carboxylic acid or derivative thereof, for example acrylic acid.
  • the polymer may be a copolymer of polyvinyl phosphonic acid and acrylic acid.
  • Polymers useful as scale inhibitors according to embodiments disclosed herein may be prepared via any suitable method known in the art for preparing such polymers. Polymers may be prepared by a radical polymerization method. Radical polymerization may be performed by contacting a reaction medium comprising at least one monomer with a radical initiator. The radical initiator may be any compound capable of producing a radical and initiating a radical polymerization.
  • Suitable radical initiators for radical polymerization of monomers may include, but are not limited to those, 2,2'-Azobis(2-methylpropionamidine)dihydrochloride (V-50), 4,4'-Azobis(4-cyanovaleric acid) (V-501), 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride (V-044), sodium persulfate (Na2S20s), ammonium persulfate ((NH4)2S20S), or hydrogen peroxide (H2O2).
  • V-50 2,2'-Azobis(2-methylpropionamidine)dihydrochloride
  • V-501 4,4'-Azobis(4-cyanovaleric acid)
  • V-044 2,2'-Azobis[2-(2-imidazolin-2- yl)propane]dihydrochloride
  • Na2S20s sodium persulfate
  • the copolymer may comprise at least one monomer (A) in an amount of at least 10 mol%, 20 mol%, 30 mol%, 40 mol% or 50 mol% and of at most 50 mol%, 60 mol%, 70 mol%, 80 mol% or 90 mol% where any lower limit can be used in combination with any upper limit.
  • the copolymer may comprise at least one monomer (A) in an amount of 10 to 90 mol%, preferably of 20 to 80 mol%.
  • the copolymer may comprise at least one monomer (B) in an amount of at least 10 mol%, 20 mol%, 30 mol%, 40 mol% or 50 mol% and of at most 50 mol%, 60 mol%, 70 mol%, 80 mol% or 90 mol% where any lower limit can be used in combination with any upper limit.
  • the copolymer may comprise at least one monomer (B) in an amount of 10 to 90 mol%, preferably of 20 to 80 mol%.
  • the copolymer may comprise at least one comonomer in an amount of at least 10 mol%, 20 mol%, 30 mol%, 40 mol% or 50 mol% and of at most 50 mol%, 60 mol%, 70 mol%, 80 mol% or 90 mol% where any lower limit can be used in combination with any upper limit.
  • the copolymer may comprise at least one comonomer in an amount of 10 to 90 mol%, preferably of 20 to 80 mol%.
  • Polymers according to embodiments may have a number average molecular weight (Mn) or a weight average molecular weight (M w ) (here defined as molecular weight) ranging from a lower limit of at least 300 g/mol, 400 g/mol, 500 g/mol, 1000 g/mol, 1500 g/mol, 2000 g/mol, 3000 g/mol, 4000 g/mol, 5000 g/mol, 6000 g/mol, 7000 g/mol, 8000 g/mol, 9000 g/mol, 10000 g/mol, 15000 g/mol, or 20000 g/mol, to an upper limit of at most 30000 g/mol, 40000 g/mol, 50000 g/mol, 60000 g/mol, 70000 g/mol, 80000 g/mol, 90000 g/mol, or 100000 g/mol where any lower limit can be used in combination with any upper limit.
  • the polymers have a molecular weight
  • Molecular weight (Mn and M w ) of polymers may be determined by suitable method known in the art. Molecular weight (Mn and M w ) of polymers may in particular be determined by size exclusion chromatography (SEC) calibrated with polyethylene oxide) standards.
  • SEC size exclusion chromatography
  • Polymers according to embodiments may have a poly dispersity index (PDI), as a measure of the broadness of a molecular weight, defined by M w /M n ratio, ranging from a lower limit of at least 1.1, 1.2, 1.3, 1.4, 1.5, 1.75, or 2 to an upper limit of at most 2, 3, 4, 5, 6, or 7 where any lower limit can be used in combination with any upper limit.
  • PDI poly dispersity index
  • methods for inhibiting titanate scale in an industrial process may including contacting a reaction medium with a scale inhibitor comprising a polymer having phosphonate functional groups.
  • the scale inhibitor may be a blend of at least two polymers.
  • the blend of at least two polymers comprises at least one polymer having phosphonate functional groups.
  • the at least one polymer having phosphonate functional groups in the blend is selected from the group consisting of vinylphosphonic acid polymer, vinylphosphonic acid: acrylic acid copolymer, polyethyleneimine phosphonic acid polymer, polyethyleneimine phosphonic acid copolymer, and combinations thereof.
  • the industrial process may be a Bayer process for refining alumina from bauxite ore.
  • the Bayer process may be a single stream process.
  • the reaction medium may be a Bayer process liquor or a bauxite feed slurry.
  • the scale inhibitor may be added to the liquor or slurry before bauxite digestion, or may be added during the digestion.
  • the scale inhibitor is added at a reaction temperature of at least 40°C, in particular of at least 60 °C and of at most 300 °C.
  • the scale inhibitor may be introduced to the feed slurry in bauxite slurry heaters at -100 °C.
  • the scale inhibitor may be introduced inside the heating train comprising the heaters at -200 °C.
  • the scale inhibitor may be present in the reaction medium in an amount of at least 5 ppm, 10 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 1000 ppm, or 2000 ppm and of at most 2000 ppm, 3000 ppm, 4000 ppm, or 5000 ppm where any lower limit can be used in combination with any upper limit.
  • the scale inhibitor may be present in an amount of 5 to 5000 ppm, preferably from 100 to 2500 ppm.
  • a polymerization procedure may be adapted from a synthesis reported by Blandford et al. US 7,862, 727 B2.
  • a solution of VPA monomer at a desired compositional mole % is prepared in DI water at a concentration of 25 - 75 wt% and charged to a round bottom flask.
  • Solutions of the radical initiator, with an amount depending on the target molar mass, in DI water at 7 - 17 wt%; and a solution of AA monomer, at a desired compositional mole %, in DI water at 60 - 80 wt% are prepared in separate syringes for charging.
  • the reaction vessel is purged and maintained under nitrogen and the reactor temperature is set to a value in the range of 50 - 110 °C.
  • AA solution is added continuously over 5 - 13 hrs.
  • the initiator solution is added continuously for 30 min longer than the addition time of the AA solution.
  • the final concentration of the monomers in the reaction mixture as free acids is typically in the range of 30 - 50 wt%.
  • the reaction mixture is then cooled to room temperature to yield a yellow solution.
  • Polyethyleneimine is a commercially available branched polymer from Nippon Shokubai Co., Ltd. at molar mass of 300 Da (300 g/mol), 600 Da (600 g/mol), 1200 Da (1200 g/mol), 1800 Da (1800 g/mol), 10 kDa (10000 g/mol), 30 kDa (30000 g/mol), and 70 kDa (70000 g/mol).
  • Post-polymerization modification of the commercially available polyethylene imine (PEI) was adapted from a synthesis reported by Smith et al., US5766478A. In a representative example, a mixture of PEI (EPOMIN, SP-018; 10 g, 5.4 mmol), cone.
  • HC1 (37%, 12.1 N; 51 g, 0.52 mol) and DI water (67 g) is prepared at room temperature.
  • Solid phosphorous acid (19 g, 0.23 mol) is added into the mixture and dissolved completely.
  • the reaction temperature is set to 80 °C. Once the temperature reaches to 80 °C, formaldehyde solution (37%, 41.4 g, 0.51 mol) is added into the reaction flask dropwise over an hour. After the addition is completed, the reaction temperature is kept at 80 °C for another hour and then cooled down to room temperature. The mixture is stirred at room temperature overnight to yield a dark red solution. The final pH of the solution is adjusted to ca. 7.
  • the conversion of VP A is determined by 31 P NMR using the broad polymer peak at 30 ppm and residual VPA peak at 15 ppm.
  • the conversion of AA monomer is calculated by the information from 1 H NMR and 31 P NMR.
  • Molecular weight of polymers are determined by size exclusion chromatography (SEC) calibrated with poly(ethylene oxide) standards.
  • Group 1 polymers are terpolymers of vinylphosphonic acid (VP A), acrylic acid (AA) and dimethyl acrylamide (DMA).
  • Group 2 polymers are co-polymers of vinylphosphonic acid (VP A) and acrylic acid (AA).
  • Group 3 polymers are co-polymers of vinylphosphonic acid (VP A) and dimethyl acrylamide (DMA).
  • Group 4 polymers are polymers of vinylphosphonic acid (VPA) and N-isoproyl acrylamide (NiPAM).
  • Performance is calculated as the % of remaining scale upon addition of phosphonic acid based polymers (ppm calculated as volume of active polymer in pL relative to total volume in L) at a reaction temperature of 213 °C and a residence time of 65 min. This table illustrates that the fact that performance can vary depending on the composition of the copolymer and the mol% of each monomer.
  • Table 1 provides performance testing of phosphonate-containing scale inhibitors, comparative Ex. 1-6, compared with a co-polymer of phosphonic acid and acrylic acid (Ex. 4). Performance is calculated as the % of remaining scale upon addition of small molecule or polymeric phosphonate-containing scale inhibitors (ppm calculated as volume of active polymer in pL relative to total volume in L) at a reaction temperature of 213 °C and a residence time of 65 min. Small molecule structures, including the free monomer, failed to inhibit the formation of calcium titanate scale.
  • Table 3 provides scale inhibition performance of various vinylphosphonic acid (VP A) and acrylic acid (AA) co-polymers, where the mol% of each monomer is varied. Performance is calculated as the % of remaining scale upon addition of various poly(vinylphosphonic acid-co-acrylic acid) polymers (ppm calculated as volume of active polymer in pL relative to total volume in L) at a reaction temperature of 213 °C and a residence time of 65 min. This table illustrates the impact of %VPA on improving performance.
  • Table 4 provides performance testing of polyethylenimine (PEI)-phosphonic acid polymer (Ex. 17), compared with a co-polymer of phosphonic acid and acrylic acid (Ex. 14). Performance is calculated as the % of remaining scale upon addition of phosphonic acid based polymers (ppm calculated as volume of active polymer in pL relative to total volume in L) at a reaction temperature of 180 °C and a residence time of 15 min. PEI- phosphonic acid modified polymer shows comparable performance to the phosphonic acid and acrylic acid copolymer.
  • PEI polyethylenimine
  • Table 4 provides performance testing of a vinylphosphonic acid (VP A) and acrylic acid (AA) co-polymer using synthetic Bayer liquor (e.g. here 117 g/L AI2O3, 450 g/L Na2CCh, 470 g/L Na2CCh) instead of NaOH solution. Performance is calculated as the % of remaining scale upon addition of poly(vinylphosphonic acid-co-acrylic acid) polymer (ppm calculated as volume of active polymer in pL relative to total volume in L) at a reaction temperature of 213 °C and a residence time of 60 min.
  • synthetic Bayer liquor e.g. here 117 g/L AI2O3, 450 g/L Na2CCh, 470 g/L Na2CCh

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Abstract

L'invention concerne un procédé d'inhibition d'incrustation d'écailles contenant du titane dans un procédé industriel. Le procédé comprend la mise en contact d'un milieu réactionnel dans le processus avec un inhibiteur d'incrustation comprenant un polymère comprenant des groupes fonctionnels phosphonates pendants. Les polymères comprenant peuvent être soit des homopolymères, des copolymères, soit un mélange de polymères comprenant des unités récurrentes comprenant les groupes fonctionnels phosphonates pendants.
PCT/EP2023/080854 2022-11-04 2023-11-06 Inhibition d'incrustation de titanate dans un processus bayer à flux unique Ceased WO2024094892A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0401833A2 (fr) * 1989-06-08 1990-12-12 National Starch and Chemical Investment Holding Corporation Polymères renfermant un aminophosphonate
US5534235A (en) * 1995-09-05 1996-07-09 Nalco Chemical Company Polymers containing phosphonic acid groups for the treatment of red mud in the Bayer process
US5733460A (en) * 1996-04-29 1998-03-31 Cytec Technology Corp. Use of hydroxamated polymers to alter Bayer Process scale
US5766478A (en) 1995-05-30 1998-06-16 The Regents Of The University Of California, Office Of Technology Transfer Water-soluble polymers for recovery of metal ions from aqueous streams
US7862727B2 (en) 2004-02-13 2011-01-04 General Electric Company Desalination scale inhibitors

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0401833A2 (fr) * 1989-06-08 1990-12-12 National Starch and Chemical Investment Holding Corporation Polymères renfermant un aminophosphonate
US5766478A (en) 1995-05-30 1998-06-16 The Regents Of The University Of California, Office Of Technology Transfer Water-soluble polymers for recovery of metal ions from aqueous streams
US5534235A (en) * 1995-09-05 1996-07-09 Nalco Chemical Company Polymers containing phosphonic acid groups for the treatment of red mud in the Bayer process
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