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WO2012128755A1 - Prévention ou réduction de la formation de tartre dans la production d'acide phosphorique dans un procédé humide - Google Patents

Prévention ou réduction de la formation de tartre dans la production d'acide phosphorique dans un procédé humide Download PDF

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Publication number
WO2012128755A1
WO2012128755A1 PCT/US2011/029319 US2011029319W WO2012128755A1 WO 2012128755 A1 WO2012128755 A1 WO 2012128755A1 US 2011029319 W US2011029319 W US 2011029319W WO 2012128755 A1 WO2012128755 A1 WO 2012128755A1
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Prior art keywords
acid
chosen
scale
phosphoric acid
ton
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PCT/US2011/029319
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English (en)
Inventor
Sathanjheri Ravishankar
Bing Wang
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Cytec Technology Corp
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Cytec Technology Corp
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Priority to EP11712724.1A priority Critical patent/EP2688837A1/fr
Priority to CA2830875A priority patent/CA2830875A1/fr
Priority to EA201391360A priority patent/EA025200B1/ru
Priority to CN201180069454.9A priority patent/CN103429528B/zh
Priority to AP2013007112A priority patent/AP2013007112A0/xx
Priority to PCT/US2011/029319 priority patent/WO2012128755A1/fr
Priority to MX2013010468A priority patent/MX358775B/es
Priority to AU2011363047A priority patent/AU2011363047A1/en
Priority to MA36335A priority patent/MA35044B1/fr
Priority to BR112013024257A priority patent/BR112013024257A2/pt
Application filed by Cytec Technology Corp filed Critical Cytec Technology Corp
Priority to PH1/2013/501956A priority patent/PH12013501956A1/en
Publication of WO2012128755A1 publication Critical patent/WO2012128755A1/fr
Priority to IL228352A priority patent/IL228352A0/en
Priority to TNP2013000369A priority patent/TN2013000369A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
    • 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

Definitions

  • the invention relates to formulated reagents and methods for preventing or reducing scale formation in and/or on production equipment at the different stages of the phosphoric acid production process.
  • phosphoric acid can be prepared by three routes - the thermal process, the wet process, and the dry kiln process - the wet process is the most commonly-used process in phosphoric acid production.
  • calcium phosphate rocks which contain mostly calcium phosphate, are cleaned in the wash plant and grinded in the Ball mill before fed into a series of reactors for digestion with sulfuric acid along with recycled phosphoric acid from the process.
  • the digestion temperature typically ranges from 40°C to 80°C.
  • the process stream is washed with evaporator condensate while being forced through a filter.
  • the reaction slurry is filtered to separate phosphoric acid from Gypsum (calcium sulfate).
  • Gypsum calcium sulfate
  • the filtered, crude phosphoric acid is then sent to Clarifiers and Evaporators for further purification and concentration.
  • the purified phosphoric acid is either sent out as Merchant Grade Acid (MGA) or continued to make 69% ⁇ 2 0 5 Super Phosphoric Acid (SPA).
  • MCA Merchant Grade Acid
  • SPA Super Phosphoric Acid
  • the Gypsum is washed and dried before being sold for commercial uses.
  • Some of the crude phosphoric acid is concentrated to 44% (P 2 0 5 ) before sent for Mono ammonium Phosphate (MAP), Diammonium Phosphate (DAP) and ammonium phosphate- sulfate (APS) production.
  • MAP Mono ammonium Phosphate
  • DAP Diammonium Phosphate
  • APS ammonium phosphate- sul
  • fluorosilicate is one of the more common scale species found in phosphoric acid production. It can be depicted by the following equations:
  • this approach is normally done by adding reagents to change the degree of supersaturation, either to induce precipitation before filtration, or to prevent scale from forming.
  • This is the preferred approach because it requires a limited amount of capital investment and does not alter the existing process in the phosphoric acid plants. It also does not require a large amount of reagent and is therefore considered both environmental, and to have a minimal impact downstream.
  • water boiler systems differ vastly from the wet-process phosphoric acid production environment, this system does not provide the best model for use in the phosphoric acid production process.
  • the water boiler systems usually have mild condition with a pH in the range of 8 to 9, and a low concentration of dissolved salts.
  • the wet-process phosphoric acid production environment by contrast, normally contains harsh conditions with a low pH and a high solid content.
  • the scale in phosphoric acid plants have much more complicated components— containing more than 15 known species, such as Na 2 SiF 6 , K 2 SiF 6 , CaSiF 6 .2H 2 0, CaF 2 , MgF 2 , CaS0 4 .2H 2 0 (Gypsum), MgSiF 6 .6H 2 0, Mgo .8 Ali.5F6.XH 2 O (wherein X is a variable integer), MgH 2 P 6 0 7 , CaS0 4 , A1(P0 3 ) 3 , NaK 2 AlF 6 , Ca 3 (AlF 6 ) 2 .4H 2 0, MgNaAlF 6 .2H 2 0, Ca 4 SO 4 AlSiF 13 .10H 2 O (see for example, A.
  • a 60 torr vacuum is applied in a boiler and 85°C phosphoric acid is circulating and heated up by a heat exchanger at 130°C.
  • some scale is formed either at the boiler or at the heat exchanger.
  • the scale formed at the boiler can be different than that formed at the heat exchanger.
  • the slow forming scale such as that formed at the heat exchanger, contain mostly magnesium fluoro- aluminates; while the fast forming scale such as that formed on pipes, contain mostly sodium or potassium fluorosilicate.
  • 5,120,519 discloses that high molecular weight polyacrylamide and polyacrylic acid can prevent scale from adhering on the surface of the phosphate rock and phosphoric acid.
  • the use of most of these chemicals is not new and has been applied in the water treatment system for scale control, and the mechanism of these reagents is based mostly on their dispersant effect.
  • compositions and methods presently available for preventing and/or reducing scale in the phosphoric acid production process require further improvement.
  • Compositions and formulations that effectively prevent and/or reduce scale, thereby enabling the phosphoric acid production plant to run longer without shutting down to remove scale would be a useful advance in the art and could find rapid acceptance in the industry.
  • the invention provides methods for preventing or reducing at least one species of scale in a wet-process phosphoric acid production process by adding at one or more steps of the phosphoric acid production process an effective amount of a scale inhibiting reagent chosen from one or more of:
  • a phosphonic acid derivative chosen from: phenylphosphonic acid
  • phosphonoacetic acid hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); and mixtures thereof;
  • sulfonic acid or a corresponding derivative chosen from: sulfosuccinic acid; 5-sulfosalicylic acid hydrate; 4-sulfophthalic acid; N-(l,l-dimethyl-2- hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO); 3-amino-4- hydroxybenzenesulfonic acid; 1-dodecanesulfonic acid sodium salt; 3-sulfopropyl acrylate potassium salt; 4-hydroxybenzenesulfonic acid solution; 4,5- dihydroxynaphthalene-2,7-disulfonic acid disodium salt; hydroquinonesulfonic acid potassium salt; and mixtures thereof;
  • R 1 is chosen from H or OH; and R 2 is chosen from:— COOH; a CrC 6 carboxyalkyl or a C 2 -C6 carboxyalkenyl group; and
  • a polysaccharide comprising a sulfate, sulfonic acid or carboxylic acid functional group
  • a copolymer comprising a first repeating unit containing a functional group chosen from (i) - (iv) and a second repeating unit having a sulfonic acid or carboxylic acid functional group;
  • the reagent can also be blended with various polymers, which are known to those skilled in the art to which the invention pertains.
  • the present invention is based in part on the use of water-soluble functional organic reagents for use in preventing or reducing scale formed in and/or on the production equipment in the phosphoric acid production process.
  • phosphonic acid derivative As used herein the term "phosphonic acid derivative,” “sulfonic acid derivative,” and “carboxylic acid derivative” refer to compounds having a functional phosphonic acid, sulfonic acid, or carboxylic acid group, respectively, in the compound. Where a phosphonic acid or sulfonic acid appear together with a carboxylic acid in the same compound, the compound will be termed a phosphonic acid derivative or sulfonic acid derivative as the case may be.
  • sulfosuccinic acid is considered a sulfonic acid derivative for purposes of this application.
  • phosphonoacetic acid and 2-phosphonobutane- 1,2,4- tricarboxylic acid (PBTCA) are considered phosphonic acid derivatives for purposes of this application.
  • alkyl means a straight or branched chain hydrocarbon containing from 1 to 12 carbon atoms.
  • Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2- dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.
  • alkenyl means a straight or branched chain hydrocarbon containing from 2 to 12 carbons and containing at least one carbon-carbon double bond formed by the removal of two hydrogens.
  • Representative examples of alkenyl include, but are not limited to, ethenyl, 2-propenyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, 5-hexenyl, 2-heptenyl, 2-methyl-l-heptenyl, 3-decenyl, etc.
  • carboxyalkyl means a carboxy group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein.
  • Representative examples of carboxyalkyl include, but are not limited to,
  • carboxyalkenyl means a carboxy group, as defined herein, appended to the parent molecular moiety through an alkenyl group, as defined herein.
  • copolymer refers to a polymer composed of two or more different units, wherein the units are linked randomly or in repeating sequences, or in blocks, or as side chains off the main chain.
  • a phosphonic acid derivative copolymer refers to a copolymer having a phosphonic acid derivative unit (i.e., a first unit) linked randomly or in repeating sequence with one or more different unit (i.e., a second unit).
  • a reagent or “scale inhibiting reagent” is intended to include salts and solvates of that reagent as well as any stereoisomeric form, or a mixture of any such forms of that reagent in any ratio.
  • salts may be prepared from acceptable non-toxic acids including inorganic and organic acids.
  • Suitable acid addition salts for the reagents of the present invention include acetic, benzenesulfonic (besylate), benzoic, camphorsulfonic, citric, ethenesulfonic, fumaric, gluconic, glutamic, hydrobromic, hydrochloric, isethionic, lactic, maleic, malic, mandelic, methanesulfonic, mucic, nitric, pamoic, pantothenic, phosphoric, succinic, sulfuric, tartaric acid, p-toluenesulfonic, and the like.
  • suitable acceptable base addition salts for the reagents of the present invention include metallic salts made from aluminum, calcium, lithium, magnesium, potassium, sodium and zinc or organic salts made from lysine, N,N'-dibenzylethylenediamine, diethanolamine, and ethylenediamine.
  • the invention provides methods for preventing or reducing at least one species of scale in a wet-process phosphoric acid production process by adding at one or more steps of the phosphoric acid production process an effective amount of a scale inhibiting reagent chosen from one or more of:
  • a phosphonic acid derivative chosen from: phenylphosphonic acid
  • phosphonoacetic acid hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); and mixtures thereof;
  • sulfonic acid or a corresponding derivative chosen from: sulfosuccinic acid; 5-sulfosalicylic acid hydrate; 4-sulfophthalic acid; N-(l,l-dimethyl-2- hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO); 3-amino-4- hydroxybenzenesulfonic acid; 1-dodecanesulfonic acid sodium salt; 3-sulfopropyl acrylate potassium salt; 4-hydroxybenzenesulfonic acid solution; 4,5- dihydroxynaphthalene-2,7-disulfonic acid disodium salt; hydroquinonesulfonic acid potassium salt; and mixtures thereof;
  • R 1 is chosen from H or OH; and R 2 is chosen from:— COOH; a CrC 6 carboxyalkyl or a C 2 -C6 carboxyalkenyl group; and
  • a polysaccharide comprising a sulfate, sulfonic acid or carboxylic acid functional group
  • a copolymer comprising a first repeating unit containing a functional group chosen from (i) - (iv) and a second repeating unit having a sulfonic acid or carboxylic acid functional group;
  • LCST critical solution temperature phase transition
  • the species of scale prevented or inhibited from forming during the phosphoric acid production process includes, but is not limited to, one or more of: Si 2 F 6 ; Na 2 SiF 6 ; K 2 SiF 6 ; CaSiF6/2 H 2 0; CaF 2 ; MgF 2 ; CaS0 4 /2 H 2 0; MgSiF 6 /6 H 2 0; MgasAl ⁇ sFe/X H 2 0 (wherein X is an integer ranging from 2 to 20); MgH 2 P 6 0 7 ; CaS0 4 ; A1(P0 3 ) 3 ; NaK 2 AlF 6 ; Ca 3 (AlF 6 ) 2 /4 H 2 0; MgNaAlF 6 /2 H 2 0; and Ca 4 SO 4 AlSiF 13 /10 H 2 0.
  • the scale inhibiting reagent can be added at any step of the phosphoric acid production process, which steps are well known to those skilled in the art.
  • An overall view of the manufacture of phosphates and phosphoric acid is treated by Becker in Phosphates and Phosphoric Acids, Marcel Dekker, Inc. 1989; and by Stack in Phosphoric Acid, Part 1 and Part 2, Marcel Dekker, inc. 1968.
  • the adding step occurs at one or more of the milling step; the digesting step; the filtering step; the clarifying step; and the condensation/evaporation step of the phosphoric acid production process.
  • the adding step occurs after the digesting step of the phosphoric acid production process.
  • the adding step occurs at the
  • the scale inhibiting reagent can be added to any of the piping connecting the various stages of the phosphoric acid production process. This is sometimes referred to as the
  • the scale inhibiting reagent(s) may be intermixed in the phosphoric acid production process in various ways, e.g., in a single stage, in multiple stages, sequentially, in reverse order, simultaneously, or in various combinations thereof.
  • the scale inhibiting reagent is added to form a pre-mix, then intermixed with the phosphoric acid.
  • the scale inhibiting reagent is formed in situ by separately inter-mixing the components of the reagent with the phosphoric acid.
  • the scale inhibiting reagent (such as those embodied by Examples 16-26 and 42) can either be added to the phosphoric acid production process as a single component or as individual components anywhere along the process. Various modes of addition will be found to be effective.
  • the scale inhibiting reagents that are in liquid form may be formulated in various ways, e.g., the solid reagent may be suspended (e.g., colloidal suspension), dispersed and/or slurried in the liquid, and/or the reagent may be suspended, dispersed, slurried and/or dissolved in the liquid.
  • the reagent is added separately to the phosphoric acid solution.
  • the reagent is premixed and added together to the phosphoric acid solution.
  • the concentration of the scale inhibiting reagent added to the phosphoric acid production process is from 10 to 5000 g per ton of phosphoric acid (e.g. , 10 g/ton, 20 g/ton, 30 g/ton, 40 g/ton, 50 g/ton, 60 g/ton, 70 g/ton, 80 g/ton, 90 g/ton, 100 g/ton, 110 g/ton, 120 g/ton, 130 g/ton, 140 g/ton, 150 g/ton, 160 g/ton, 170 g/ton, 180 g/ton, 190 g/ton, 200 g/ton, 210 g/ton, 220 g/ton, 230 g/ton, 240 g/ton, 250 g/ton, 260 g/ton, 270 g/ton, 280 g/ton,
  • the concentration of the scale inhibiting reagent added to the phosphoric acid production process is from 50 to 300 g/ton of phosphoric acid. In a preferred embodiment, the concentration of the scale inhibiting reagent added to the phosphoric acid production process is 100 g/ton of phosphoric acid.
  • the treatment times and effective amounts may vary, depending in many cases on the nature of the scale formation rate and/or the species of the scale. For example, if the scale is formed within 30 minutes of the treatment, the overall treatment time may be just one hour. If the scale is not formed within 4 hours of the treatment, the overall treatment time may be over one day. One of ordinary skill in the art would be able to determine the applicable treatment time and effective amount through no more than routine means. [0041] In one embodiment, the scale formed in the phosphoric acid production process is prevented or reduced from 5 to 180 days, depending on the amount and type of scale.
  • the pH of the phosphoric acid should not be altered by a value of 1 after the addition of the reagent for treatment.
  • the preferred pH of the phosphoric acid should be in the range of 1-5 before starting the method of the invention. In case the pH of the phosphoric acid dropped below 1, it can be adjusted by sodium hydroxide or soda ash. In case the pH of the phosphoric acid rose above 5, it can be adjusted by addition of sulfuric acid or phosphoric acid.
  • the scale inhibiting reagent is a phosphonic acid derivative chosen from: phenylphosphonic acid; phosphonoacetic acid;
  • HEMPA hydroxyethylamino-di(methylene phosphonic acid)
  • the water-soluble, functional organic scale [0044] in another embodiment, the water-soluble, functional organic scale
  • inhibiting reagent is sulfonic acid or a sulfonic acid derivative chosen from:
  • sulfosuccinic acid 5-sulfosalicylic acid hydrate; 4-sulfophthalic acid; N-(l,l- dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO); 3- amino-4-hydroxybenzenesulfonic acid; 1-dodecanesulfonic acid sodium salt; 3- sulfopropyl acrylate potassium salt; 4-hydroxybenzenesulfonic acid solution; 4,5- dihydroxynaphthalene-2,7-disulfonic acid disodium salt; hydroquinonesulfonic acid potassium salt; and mixtures thereof.
  • AMPSO N-(l,l- dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid
  • 3- amino-4-hydroxybenzenesulfonic acid 1-dodecanesulfonic acid sodium salt
  • 3- sulfopropyl acrylate potassium salt 4-hydroxybenzenesulfonic acid
  • the scale inhibiting reagent is a carboxylic acid derivative chosen from:
  • R 1 is chosen from H or OH; and R 2 is chosen from:— COOH; a C C 6 carboxyalkyl or a C 2 -C 6 carboxyalkenyl group; and
  • the scale inhibiting reagent can be a carboxylic acid derivative chosen from: 3,4-dihydroxyhydrocinnamic acid; 3,4-dihydroxybenzoic acid; gallic acid; caffeic acid; and mixtures thereof.
  • the scale inhibiting reagent can be a phosphite derivative such as, but not limited to, tannic phosphite.
  • the scale inhibiting reagent can be a polysaccharide containing a sulfate, sulfonic acid or carboxylic acid functional group.
  • the polysaccharide contains a sulfate functional group and is carrageenan. While “carrageenan” is used generally to describe the different members of the family, one of skill in the art will appreciate that the family includes multiple varieties of carrageenan, and as used herein the general terms shall refer to all those that contain a sulfated functional group as part of the structure.
  • a commercially available form of carrageenan such as iota, kappa, or lambda, is used.
  • the polysaccharide scale inhibiting reagent useful for the present invention will contain a carboxy functional group and can be alginic acid, or corresponding salts thereof.
  • the polysaccharide containing a carboxy functional group can be carboxymethyl cellulose.
  • the carboxymethyl cellulose useful as a scale inhibiting reagent has a molecular weight of from 2 kDa to 100 kDa (e.g.,2 kDa; 5 kDa; 7 kDa; 10 kDa; 15 kDa; 20 kDa; 25 kDa; 30 kDa; 40 kDa; 45 kDa; 50 kDa; 55 kDa; 60 kDa; 65 kDa; 70 kDa; 75 kDa; 80 kDa; 85 kDa; 90 kDa; 95 kDa; 100 kDa).
  • 2 kDa to 100 kDa e.g.,2 kDa; 5 kDa; 7 kDa; 10 kDa; 15 kDa; 20 kDa; 25 kDa; 30 kDa; 40 kDa; 45 kDa; 50 kDa; 55
  • a carboxymethyl cellulose scale inhibiting reagent is preferred to have a molecular weight of from 10 kDa to 75 kDa. In another embodiment, a molecular weight of carboxymethyl cellulose of from 10 kDa to 30 kDa is preferred.
  • the water-soluble, functional organic scale inhibiting reagent is a co-polymer comprising a first repeating unit containing a phosphonic acid derivative, a sulfonic acid derivative, a carboxylic acid derivative, or a phosphite derivative, and a second repeating unit chosen from any suitable polymer including, but not limited to: polyethyleneimine-epoxy-hydroxysuccinate;
  • acrylamide/acrylate copolymer (CYANAMER P-70® available from Cytec Industries Inc., Woodland Park, NJ); allyl sulfonic acid/maleic anhydride copolymer
  • PAA polyacrylic acid
  • PAAS sodium polyacrylate
  • MPMA methoxyphenyl maleamic acid
  • MPMA methoxyphenyl maleamic acid
  • MA-AA maleic anhydride acrylic acid polymer
  • AMPS AA-MA-acrylamido-methyl-propane sulfonate polymer
  • any of the reagents and/or co-polymers can be further blended with a suitable polymer such as those described herein.
  • the scale inhibiting reagent can be chosen from a polymer or copolymer having a low critical solution
  • a scale inhibiting reagent having a LCST of from 30 °C to 100 °C can include a poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG) copolymer.
  • LCST is dependent upon polymer degree of polymerization, polydispersity, and branching. Accordingly, the ratio of poly(ethylene glycol) units to poly(propylene glycol) units will be determined by whether the resulting LCST is in the appropriate and desired range as described herein.
  • the scale inhibiting reagent having a LCST of from 30 °C to 100 °C can include poly(n-isopropylacrylamide) (NIP AM).
  • NIP AM poly(n-isopropylacrylamide)
  • the NIP AM can be copolymerized with acrylic acid such that the ratio of acrylic acid (AA) : NIP AM can range from 20:80 to 80:20.
  • the ratio of AA:NIPAM can be 50:50. It will be understood by those of skill in the art that copolymerizing acrylic acid with NIP AM will generally increase the hydrophillicity of the copolymer and that an increased hydrophillicity will result in an increased LCST temperature. Accordingly, the ratio of acrylic acid to NIP AM is able to be modified so it can be within the LCST range as described herein.
  • the scale inhibiting reagent is a blend comprising an organic acid, a polyamine, and a sugar acid.
  • Organic acids suitable for use in a blend reagent of the instant invention include those known to one of skill in the art.
  • the organic acid of the reagent blend is a phosphonic acid chosen from: phenylphosphonic acid; phosphonoacetic acid; hydroxyethylamino- di(methylene phosphonic acid) (HEMPA); amino-tri(methylene phosphonic acid) (ATMPA); l-hydroxyethylidene-l,l-diphosphonic acid (HEDPA);
  • DTPMP diethylenetriamine-penta(methylene phosphonic acid)
  • ETMP ethylenediamine methylene phosphonic acid
  • HPAA hydroxyl ethane phosphonothyl acetic acid
  • PBTCA phosphonobutane-l,2,4-tricarboxylic acid
  • Polyamines suitable for use in a reagent blend of the instant invention include those known to one of skill in the art.
  • the polyamine of the reagent blend can be poly-diallyl dimethyl ammonium chloride (SUPERFLOC C587®) or poly-dimethylamine epichlorohydrin ethylenediamine (SUPERFLOC C573®).
  • Sugar acids suitable for use in a reagent blend of the instant invention include those known to one of skill in the art.
  • the sugar acid is chosen from: glyceric acid; xylonic acid; gluconic acid; ascorbic acid; neuraminic acid; ketodeoxyoctulo sonic acid; glucuronic acid; galacturonic acid; iduronic acid; tartaric acid; mucic acid; saccharic acid; and mixtures thereof.
  • the reagent comprises a blend that can include l-hydroxyethylidene-l,l-diphosphonic acid (HEDPA), poly-diallyl dimethyl ammonium chloride (SUPERFLOC C587®), and gluconic acid. While the ratio of components in the reagent blend necessary to reduce or prevent scale can be readily determined by those of ordinary skill in the art with no more than routine
  • particularly preferred reagents for use in the methods of the invention include, for example, one or more of phosphonoacetic acid; tannic phosphite; hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); sulfonic acid; sulfosuccinic acid; 5-sulfosalicyclic acid hydrate; N-(l,l-dimethyl-2- hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO); 3-sulfopropyl acrylate potassium salt; 1-dodecanesulfonic acid sodium salt; 4- hydroxybenzenesulfonic acid solution; 4,5,-dihydroxynaphthalene-2,7-disulfonic acid disodium salt; 3,4-dihydroxyphenylacetic acid; 3,4-dihydroxyhydrocinnamic acid; 3,4-dihydroxybenzoic acid; tartaric acid;
  • HEDPA poly-diallyl dimethyl ammonium chloride
  • SUPERFLOC C587® poly-diallyl dimethyl ammonium chloride
  • gluconic acid and mixtures thereof.
  • the method can further include one or more step of flocculating the phosphoric acid with a flocculating agent thereby removing the scale- causing metal ions from the phosphoric acid; treating the phosphoric acid with a precipitation agent; and filtering the phosphoric acid.
  • Typical agents for use with these additional steps are known to those of ordinary skill in the art.
  • a method for reducing or preventing scale in a wet-process phosphoric acid production process comprising:
  • a phosphonic acid derivative chosen from: phenylphosphonic acid; phosphonoacetic acid; hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); and mixtures thereof;
  • sulfosuccinic acid 5-sulfosalicylic acid hydrate; 4-sulfophthalic acid; N-(l,l- dimethyl-2-hydroxyethyl)-3-amino-2-hydroxypropanesulfonic acid (AMPSO); 3-amino-4-hydroxybenzenesulfonic acid; 1-dodecanesulfonic acid sodium salt; 3-sulfopropyl acrylate potassium salt; 4-hydroxybenzenesulfonic acid solution; 4,5-dihydroxynaphthalene-2,7-disulfonic acid disodium salt; hydroquinonesulfonic acid potassium salt; and mixtures thereof;
  • R is chosen from H or OH; and R is chosen from:— COOH; a Ci-C carboxyalkyl or a C 2 -C6 carboxyalkenyl group; and
  • a polysaccharide comprising a sulfate, sulfonic acid or carboxylic acid functional group
  • a copolymer comprising a first unit containing a functional group chosen from (i) - (iv) and a second unit having a sulfonic acid or carboxylic acid functional group;
  • LCST critical solution temperature phase transition
  • a reagent comprising a blend of an organic acid, a polyamine, and a sugar acid.
  • phosphoric acid scale is chosen from one or more of: Si 2 F 6 ; Na 2 SiF 6 ; K 2 SiF 6 ;
  • polysaccharide is chosen from: carrageenan; alginic acid; and carboxy methyl cellulose.
  • the reagent is a copolymer formulation and wherein the second repeating unit contains a functional group chosen from: polyethyleneimine-epoxy-hydroxysuccinate; acrylamide/acrylate copolymer (CYANAMER P-70®); allyl sulfonic acid/maleic anhydride copolymer (CYANAMER P-80®); poly-diallyl dimethyl ammonium chloride (SUPERFLOC C587®); poly-dimethylamine epichlorohydrin
  • phosphinopolycarboxylic acid acrylic acid/acrylate/sulfonate copolymer; polyacrylic acid (PAA); sodium polyacrylate (PAAS); methoxyphenyl maleamic acid (MPMA); maleic anhydride acrylic acid copolymer (MA-AA); AA-MA-acrylamido-methyl- propane sulfonate polymer (AMPS) hypophosphorous acid quadripolymer; AA- AMPS multipolymer; AA-acrylate copolymer T-225; and acrylic acid-2-methyl propanesulfonic acid acrylic polymer; and mixtures thereof.
  • PAA polyacrylic acid
  • PAAS sodium polyacrylate
  • MPMA methoxyphenyl maleamic acid
  • MA-AA maleic anhydride acrylic acid copolymer
  • AMPS AA-MA-acrylamido-methyl- propane sulfonate polymer
  • hypophosphorous acid quadripolymer AA-AMPS multipolymer
  • polymer or copolymer having a low critical solution temperature phase transition is chosen from: polyethyleneglycol-polypropyleneglycol- polyethyleneglycol (PEG-PPG-PEG) copolymers; poly-n-isopropyl polyacrylamide (NIP AM); and copolymers of acrylic acid-poly-n-isopropyl polyacrylamide
  • the organic acid of the reagent blend is a phosphonic acid derivative chosen from: phenylphosphonic acid; phosphonoacetic acid; hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); amino-tri(methylene phosphonic acid) (ATMPA); 1- hydroxyethylidene-l,l-diphosphonic acid (HEDPA); diethylenetriamine- penta(methylene phosphonic acid) (DTPMP); ethylenediamine methylene phosphonic acid (EDTMP); hydroxyl ethane phosphonothyl acetic acid (HPAA); and
  • a phosphonic acid derivative chosen from: phenylphosphonic acid; phosphonoacetic acid; hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); amino-tri(methylene phosphonic acid) (ATMPA); 1- hydroxyethylidene-l,l-diphosphonic acid (HEDPA); diethylene
  • PBTCA phosphonobutane-l,2,4-tricarboxylic acid
  • polyamine is poly-diallyl dimethyl ammonium chloride (SUPERFLOC C587®) or poly- dimethylamine epichlorohydrin ethylenediamine (SUPERFLOC C573®).
  • sugar acid is chosen from: glyceric acid; xylonic acid; gluconic acid; ascorbic acid; neuraminic acid; ketodeoxyoctulosonic acid; glucuronic acid;
  • galacturonic acid iduronic acid
  • tartaric acid aric acid
  • mucic acid aric acid
  • saccharic acid aric acid
  • reagent blend comprises l-hydroxyethylidene-l,l-diphosphonic acid (HEDPA), poly-diallyl dimethyl ammonium chloride (SUPERFLOC C587®), and gluconic acid.
  • HEDPA l-hydroxyethylidene-l,l-diphosphonic acid
  • SUPERFLOC C587® poly-diallyl dimethyl ammonium chloride
  • [0081] 22 A method according to any one of the preceding embodiments, wherein the concentration of the reagent is from 10 to 5000 g per ton of phosphoric acid.
  • [0082] 23 A method according to embodiment 22, wherein the concentration is from 10 to 1000 g per ton of phosphoric acid.
  • [0083] 24 A method according to embodiment 22 or embodiment 23, wherein the concentration of the reagent is 100 g per ton of phosphoric acid.
  • [0086] 27 A method according to embodiment 26, wherein the removal step is performed by flocculating the phosphoric acid with one or more flocculating agent.
  • Phosphoric acid solutions used for reagent testing are obtained from phosphoric acid plants such as Agrium, Inc. Canada (Plant A); Prayon, Inc., Georgia (Plant P); and The Mosaic Company, Florida (Plant M) at 28%, 42%, 52% or 69% P 2 O 5 .
  • ICP and XRD analysis shows the crude phosphoric acids differ greatly in their metal components, and this sometimes leads to difficulty in forming scale within a reasonable period. Accordingly, the scale formation is sometimes induced with salts. In some cases, 0.1% to 10% NaCl, KC1 or MgCl 2 salts are added to induce particular scale formation.
  • Step 1 Acid preparation - In this step, crude phosphoric acid is obtained from phosphoric acid plants and is treated properly (as is, diluting, concentrating or adding salt as scale initiator) before placing into the jacket beakers (60°C to 80°C) for 0.5 to 2 hours.
  • Step 2 Testing equipments set up and chemical addition - After the treatment, proper dosages of the functional organic reagents are added to the phosphoric acid and agitated using stir bar while being heated by water circulator at 60°C to 90°C.
  • a 316L stainless steel tube is placed in each beaker along with the cover and plastic tubings for water inlet and outlet.
  • a graphite tube or a 904L stainless steel tube can be used and the temperature for the tube can be 110 °C to 130 °C.
  • Step 3 Scale formation - If a scale inhibiting reagent is used, it can be added just before the conditioning (generally the additive is used as a solution containing 1-10% of active reagent). This solution is put into the treated phosphoric acid in the jacketed beaker and is heated with agitation at 60°C to 80°C for 30 minutes before the tube waster is turned on and kept at that temperature for 2-12 hours. Two to nine such tests (beakers) are done at one time. At the end of the test, the tube is thoroughly rinsed and dried in an oven (80°C) for 1-2 hours.
  • the additive is used as a solution containing 1-10% of active reagent. This solution is put into the treated phosphoric acid in the jacketed beaker and is heated with agitation at 60°C to 80°C for 30 minutes before the tube waster is turned on and kept at that temperature for 2-12 hours. Two to nine such tests (beakers) are done at one time. At the end of the test, the tube is thoroughly rinsed and
  • Step 4 Weighing and analysis of the scale - Considerable scale is observed to form on the steel tube.
  • the weight gain of the steel tube is a measure of the amount of scaling.
  • the weight of scale formed is expressed as a percentage of the average weight that formed on the blanks (i.e, no reagent is used) that were part of the same set of tests.
  • the total amount of scale is also a measure of antiscalant activity and this may be expressed as a percentage of the total weight that formed in the blank experiments that were part of the same set of tests.
  • the scale is also analyzed by ICP and XRD for metal ion and component information.
  • This test method is preferred because other test methods collect both the scales and the insolubles, although the insoluble may be free flowing in the acid stream in the real plant and thus not contribute as significantly to the scale growth.
  • the scale is collected on the outside surface of the stainless steel tubes. The tubes are weighed and compared to the tubes without reagent treatment to calculate the scale changes.
  • the reagents are usually prepared in deionized (“DI") water for final of 3% concentration for testing. Unless it is stated otherwise, the maximum concentration of reagent used in the testing solution is 2000 mg/kg.
  • Phosphoric acid synthetic or crude plant acid sample at 286% is mixed well before evenly dividing into 4 beakers (450-700 g). The beakers are mixed simultaneously by stir bars at the same speed. The hot plate is turned on to heat the water bath to a temperature of about 90° C. After the mixing in each beaker is stabilized, the power of the heating circulator is started. Once the temperature of the circulator reads about 50-60°C, reagents are then added to the individual beaker (usually to three of them with remaining one as control).
  • the heating for the jacket and cooling water for the tubes are turned off along with the stirring and heating for the hot plate.
  • the tubes are disconnected and rinsed in a beaker with 500 ml DI water to remove the residual phosphoric acid on the tubes.
  • the tubes are then dried in an oven for 1 hour at 80 °C and cooled to room
  • Percent scale reduction (increase) lOOx (Wt of scale w/reagent -Wt of scale w/o reagent )/( Wt of scale w/o reagent). ICP analysis and XRD analysis is submitted when necessary.
  • the testing condition is similar to that for Example 1, but the phosphoric acid concentration is increased to 52 %.
  • the test is performed with 55°C tube temperature and 80°C acid temperature or with 35°C tube temperature and 70°C acid temperature in order to increase the temperature difference to enhance scale formation.
  • 240 rpm to 300 rpm agitation 1 kg of acid and 100 ppm (3g of 3% solution) reagents is used.
  • the duration of the tests is between 2 to 6 hours.
  • a typical experimental process for hydroxypolyethylenimino succinate is as follows: 2g disodium cis-epoxysuccinate is synthesized from known procedure and is mixed with 8.3g 50% polyethylenimine (PEI) and heated (either neat or in CH 3 CN) and stirred for 4 hr. at 80 °C. After cooling, the viscous liquid is treated with hexanes after which it was solidified. It is filtered and dried and weighted. The solid is dissolved in water for concentration adjustment.
  • PEI polyethylenimine
  • the testing condition is similar to that for Example 1, except the acid concentration is 28 % or 42 %, or a synthetically made phosphoric acid solution to match the concentration of scaling species in the acid.
  • the test is performed with 130 °C tube temperature using a recirculation heater with silicone oil.
  • the acid temperature begins at room temperature, eventually rising to between 90-95 °C.
  • 240 to 300 rpm agitation, 1 kg of acid, and 100 ppm of reagent is used.
  • the duration of the tests is from 2 to 6 hours. Results are provided below.

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Abstract

La présente invention concerne des procédés de prévention ou de réduction de la formation de tartre dans un procédé de production d'acide phosphorique humide en mélangeant un réactif d'inhibition du tartre dans une ou plusieurs des étapes de la production d'acide phosphorique dans une quantité suffisante pour prévenir ou réduire la formation de tartre.
PCT/US2011/029319 2011-03-22 2011-03-22 Prévention ou réduction de la formation de tartre dans la production d'acide phosphorique dans un procédé humide Ceased WO2012128755A1 (fr)

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MA36335A MA35044B1 (fr) 2011-03-22 2011-03-22 Prévention ou réduction de la formation de tartre dans la production d'acide phosphorique dans un procédé humide
EA201391360A EA025200B1 (ru) 2011-03-22 2011-03-22 Профилактика или снижение накипи в производстве экстракционной фосфорной кислоты
CN201180069454.9A CN103429528B (zh) 2011-03-22 2011-03-22 防止或减少湿法磷酸生产中的污垢
AP2013007112A AP2013007112A0 (en) 2011-03-22 2011-03-22 Preventing or reducing scale in wet-process phosphoric acid production
PCT/US2011/029319 WO2012128755A1 (fr) 2011-03-22 2011-03-22 Prévention ou réduction de la formation de tartre dans la production d'acide phosphorique dans un procédé humide
MX2013010468A MX358775B (es) 2011-03-22 2011-03-22 Prevencion o reduccion de incrustaciones en produccion de acido fosforico de proceso humedo.
AU2011363047A AU2011363047A1 (en) 2011-03-22 2011-03-22 Preventing or reducing scale in wet-process phosphoric acid production
EP11712724.1A EP2688837A1 (fr) 2011-03-22 2011-03-22 Prévention ou réduction de la formation de tartre dans la production d'acide phosphorique dans un procédé humide
CA2830875A CA2830875A1 (fr) 2011-03-22 2011-03-22 Prevention ou reduction de la formation de tartre dans la production d'acide phosphorique dans un procede humide
BR112013024257A BR112013024257A2 (pt) 2011-03-22 2011-03-22 método para reduzir ou prevenir a incrustação em um processo de produção de ácido fosfórico em processo a úmido
PH1/2013/501956A PH12013501956A1 (en) 2011-03-22 2011-03-22 Preventing or reducing scale in wet-process phosphoric acid production
IL228352A IL228352A0 (en) 2011-03-22 2013-09-11 Prevention or reduction of stone in a wet process for the production of phosphoric acid
TNP2013000369A TN2013000369A1 (en) 2011-03-22 2013-09-18 Preventing or reducing scale in wet-process phosphoric acid production

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US9028787B2 (en) 2009-09-25 2015-05-12 Cytec Technology Corp. Preventing or reducing scale in wet-process phosphoric acid production
EA026955B1 (ru) * 2015-03-16 2017-06-30 Общество с ограниченной ответственностью "ФАРМА-ПОКРОВ" Дезинфицирующая композиция
US9902617B2 (en) 2014-02-11 2018-02-27 Cytec Industries Inc. Primary amine-containing polymers useful as scale inhibitors
US10759662B2 (en) 2018-03-12 2020-09-01 Solenis Technologies, L.P. Systems and methods for reducing formation of scale in phosphoric acid production
US10906828B2 (en) 2015-02-11 2021-02-02 Cytec Industries Inc. Modified amines useful as scale inhibitors in wet process phosphoric acid production
CN112919650A (zh) * 2021-01-21 2021-06-08 王齐繁 一种阻垢缓蚀剂、阻垢缓蚀剂用组合物及其制备方法和应用

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SG11201901465RA (en) 2016-08-25 2019-03-28 Gen Electric Reduced fouling of hydrocarbon oil
CN107043094A (zh) * 2017-04-18 2017-08-15 云南佳贝节能科技有限公司 一种浓缩磷酸的加工系统
CN111215247B (zh) * 2020-01-07 2021-04-23 中南大学 一种用于高钙萤石正浮选的抑制剂及浮选方法

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US9028787B2 (en) 2009-09-25 2015-05-12 Cytec Technology Corp. Preventing or reducing scale in wet-process phosphoric acid production
US9242863B2 (en) 2009-09-25 2016-01-26 Cytec Technology Corp. Process and reagents for the inhibition or reduction of scale formation during phosphoric acid production
US9902617B2 (en) 2014-02-11 2018-02-27 Cytec Industries Inc. Primary amine-containing polymers useful as scale inhibitors
US10214421B2 (en) 2014-02-11 2019-02-26 Cytec Industries Inc. Primary amine-containing polymers useful as scale inhibitors
CN110396149A (zh) * 2014-02-11 2019-11-01 塞特工业公司 作为抑垢剂有用的含有伯胺的聚合物
EP3623500A1 (fr) * 2014-02-11 2020-03-18 Cytec Industries Inc. Polymères contenant des amines primaires utiles en tant qu'inhibiteurs de tartre
AU2019203226B2 (en) * 2014-02-11 2021-07-29 Cytec Industries Inc. Primary amine-containing polymers useful as scale inhibitors
CN110396149B (zh) * 2014-02-11 2023-09-05 塞特工业公司 作为抑垢剂有用的含有伯胺的聚合物
US10906828B2 (en) 2015-02-11 2021-02-02 Cytec Industries Inc. Modified amines useful as scale inhibitors in wet process phosphoric acid production
EA026955B1 (ru) * 2015-03-16 2017-06-30 Общество с ограниченной ответственностью "ФАРМА-ПОКРОВ" Дезинфицирующая композиция
US10759662B2 (en) 2018-03-12 2020-09-01 Solenis Technologies, L.P. Systems and methods for reducing formation of scale in phosphoric acid production
CN112919650A (zh) * 2021-01-21 2021-06-08 王齐繁 一种阻垢缓蚀剂、阻垢缓蚀剂用组合物及其制备方法和应用

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