Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/22—Magnesium silicates

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 O 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- sulf
• fluorosilicate is one of the more common scale species found in phosphoric acid production. It can be depicted by the following equations:
• 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.
• 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 production process a water-soluble, functional organic reagent chosen from one or more of: a phosphonic acid derivative; sulfonic acid or a corresponding derivative; a carboxylic acid derivative; a phosphite derivative; a co-polymer having a first monomer chosen from any of the preceding reagents and a second monomer chosen from a suitable polymer, in an amount sufficient to prevent or reduce the scale, provided that the phosphonic acid derivative is not chosen from: 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
• ATMPA amino-tri(methylene
• PBTCA phosphonobutane-l,2,4-tricarboxylic acid
• 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.
• copolymer refers to a polymer composed of two or more different monomers, wherein the monomers 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 monomer (i.e., a first monomer) linked randomly or in repeating sequence with one or more other monomer (i.e., a second monomer).
• a reagent As used herein, and as would be understood by the person of skill in the art, the recitation of "a 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. [0025] When the reagents of the present invention are basic, 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, the method comprising: adding at one or more step of the phosphoric acid production process a water-soluble functional organic reagent chosen from one or more of: a phosphonic acid derivative; sulfonic acid or a corresponding derivative; a carboxylic acid derivative; a phosphite derivative; a co-polymer having a first monomer chosen from any of the preceding reagents and a second monomer chosen from any suitable polymer, in an amount sufficient to prevent or reduce the scale, provided that the phosphonic acid derivative is not chosen from: amino-tri(methylene phosphonic acid) (ATMPA); l-hydroxyethylidene-l,l-diphosphonic acid (HEDPA);
• ATMPA amino-tri(methylene phosphonic acid)
• HEDPA l-hydroxyethylidene-l,l-diphosphonic acid
• DTPMP diethylenetriamine-penta(methylene phosphonic acid)
• ETMP ethylenediamine methylene phosphonic acid
• HPAA hydroxyl ethane phosphonothyl acetic acid
• PBTCA phosphonobutane-l,2,4-tricarboxylic acid
• 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 water-soluble functional organic reagents can be added at any step of the phosphoric acid production process, which steps are well known to those skilled in the art.
• 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 condensation/evaporation step of the process.
• the reagent(s) may be intermixed in various ways, e.g., in a single stage, in multiple stages, sequentially, in reverse order, simultaneously, or in various combinations thereof.
• the reagent is added to form a pre-mix, then intermixed with the phosphoric acid.
• the reagent is formed in situ by separately inter-mixing the components of the reagent with the phosphoric acid.
• Various modes of addition will be found to be effective.
• the reagents that comprise a liquid 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 water-soluble functional organic reagent is from 10 to 1000 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,
• the concentration of the water-soluble functional organic reagent is from 50 to 300 g/ton of phosphoric acid. In a preferred embodiment, the concentration of the water-soluble functional organic reagent is 100 g/ton of phosphoric acid.
• the treatment times 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 through routine means.
• the scale formed in the phosphoric acid production process is prevented or reduced from 10 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 water-soluble functional organic reagent is a phosphonic acid derivative chosen from: phenylphosphonic acid; phosphonoacetic acid; hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); and mixtures thereof.
• the water-soluble functional organic reagent is 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.
• sulfonic acid derivative chosen from: sulfosuccinic acid; 5-sulfosalicylic acid hydrate; 4-sulfophthalic acid; N-(l,l-dimethyl-2-hydroxyethyl)-3
• the water-soluble functional organic reagent is a carboxylic acid derivative chosen from: 3,4-dihydroxyhydrocinnamic acid; 3,4- dihydroxybenzoic acid; gallic acid; caffeic acid; tartaric acid; and mixtures thereof.
• the water-soluble functional organic reagent is a co-polymer comprising a phosphonic acid derivative, a sulfonic acid or corresponding derivative, a carboxylic acid derivative, or a phosphite derivative as a first monomer and a second monomer chosen from any suitable polymer including, but not limited to: polyethyleneimine-epoxy-hydroxysuccinate; CYANAMER P-70® (available from Cytec Industries Inc., Woodland Park, NJ); CYANAMER P-80® (available from Cytec Industries Inc., Woodland Park, NJ); SUPERFLOC® C573, C587 (available from Cytec Industries Inc., Woodland Park, NJ); poly(4-styrenesulfonic acid);
• phosphinopolycarboxylic acid acrylic acid/acrylate/sulfonate co-polymer; polyacrylic acid (PAA); sodium polyacrylate (PAAS); methoxyphenyl maleamic acid (MPMA); maleic anhydride acrylic acid polymer (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.
• any of the reagents and/or co-polymers can be further blended with a suitable polymer such as those described herein.
• 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-hydroxybenzene sulfonic 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; polyethyleneimine-ep
• the method can further include one or more step of flocculating the phosphoric acid with a flocculating agent; leaching the phosphoric acid with a leaching agent; precipitating 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 preventing or reducing at least one species of scale in a wet-process phosphoric acid production process comprising:
• a reagent chosen from one or more of:
• ATMPA amino-tri(methylene phosphonic acid)
• HEDPA l-hydroxyethylidene-1,1- diphosphonic acid
• DTPMP diethylenetriamine-penta(methylene phosphonic acid)
• ETMP ethylenediamine methylene phosphonic acid
• HPAA hydroxyl ethane phosphonothyl acetic acid
• PBTCA phosphonobutane-l,2,4-tricarboxylic acid
• phosphoric acid scale is chosen from one or more of: Si 2 F6; Na 2 SiF 6 ; K 2 SiF 6 ;
• phosphonoacetic acid hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); and mixtures thereof.
• reagent is 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.
• sulfonic acid derivative chosen from: sulfosuccinic acid; 5-sulfosalicylic acid hydrate; 4-sulfophthalic acid; N-(l,l-dimethyl-2-hydroxyethyl)-3-amino-2-
• the reagent is a carboxylic acid chosen from: 3,4-dihydroxyphenylacetic acid; 3,4- dihydroxyhydrocinnamic acid; 3,4-dihydroxybenzoic acid; gallic acid; caffeic acid; tartaric acid; and mixtures thereof.
• PAA polyacrylic acid
• PAAS sodium polyacrylate
• reagent is chosen from: phosphonoacetic acid; hydroxyethylamino-di(methylene phosphonic acid) (HEMPA); tannic phosphite; sulfonic acid; sulfosuccinic acid; 5- sulfosalicylic 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; polyethyleneimine-epoxy-
• concentration of the reagent is from 10 to 1000 g per ton of phosphoric acid.
• a method according to embodiment 14, wherein the concentration of the reagent is from 50 to 300 g per ton of phosphoric acid.
• a method according to any of the preceding embodiments further comprising removing the scale-causing metal ions from the resulting phosphoric acid.
• a method according to any of embodiments 18 to 20 furthermore
• a method according to any one of embodiments 18 to 21 further comprising filtering the phosphoric acid.
• a method for preventing or reducing at least one species of scale in a wet-process phosphoric acid production process comprising:
• a 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;
• a method for preventing or reducing at least one species of scale in a wet-process phosphoric acid production process comprising:
• a reagent chosen from one or more of:
• 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 -
• 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 functional organic reagent to prevent or reduce scale 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.
• Step 4 Weighing and analysis of the scale - Considerable scale is
• 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 concentration reagent in the testing solution is at a maximum of 2000 ppm.
• 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 beakers are removed with clamps attached and used acid solutions are poured into a waste container.
• the beakers are cleaned and returned to their original positions for the next run.
• the stainless steel tubes are cleaned, oven dried, and weighed before reused for the next run.
• AeroDri® 104 available -55 from Cytec Industries Inc.
• 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 following: 2g disodium cis-epoxysuccinate was synthesized from known procedure and was 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 was treated with hexanes after which it was solidified. It was filtered and dried and weighted. The solid was dissolved in water for concentration adjustment. The reagent testing results are summarized in Table F and reported as percent of scale formed versus blank, where no reagent is used.
• PEI polyethylenimine

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