CN102712476A - Preventing or reducing scale in wet-process phosphoric acid production - Google Patents
Preventing or reducing scale in wet-process phosphoric acid production Download PDFInfo
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- CN102712476A CN102712476A CN2010800516585A CN201080051658A CN102712476A CN 102712476 A CN102712476 A CN 102712476A CN 2010800516585 A CN2010800516585 A CN 2010800516585A CN 201080051658 A CN201080051658 A CN 201080051658A CN 102712476 A CN102712476 A CN 102712476A
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- acid
- phosphoric acid
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- fouling
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
Abstract
Methods for preventing or reducing the formation of scale in a wet-process phosphoric acid production process by intermixing a water-soluble functional organic reagent with a phosphoric acid at one or more step of the phosphoric acid production process in an amount sufficient to prevent or reduce at least one species of scale are provided.
Description
Technical field
The present invention relates to be used to prevent or reduce among the production equipment of the different steps of production process of phosphoric acid and/or on form the formula agent and the method for fouling.
Background technology
Though phosphoric acid can prepare through 3 kinds of methods (hot method, wet method and dry kiln method), wet method is the most frequently used phosphoric acid preparation method.In the method, calcium phosphate ore (mainly comprising calcium phosphate) is washed in cleaning equipment and at ball mill grinding, infeeds then in the series reaction device, reach the phosphoric acid acidolysis (digestion) of reclaiming with sulfuric acid from said method.Acidolysis temperature typically is 40 ° of C-80 ° of C.After reaction sequence is accomplished, force through strainer simultaneously with evaporator condensation thing washing process stream.
After acidolysis, the filtering reaction slurry is to separate phosphoric acid from gypsum (calcium sulfate).Then the raw phosphoric acid that is filtered is conducted to cleaner and vaporizer in order to be further purified and to concentrate.Purified phosphoric acid is confessed as commercial grade acid (MGA), perhaps continues preparation 69%P
2O
5Peroxophosphoric acid (SPA).Gypsum is washed and is dry, sells for commercial use then.Some bullion phosphoric acid are concentrated into 44% (P
2O
5), be used to prepare primary ammonium phosphate (MAP), Secondary ammonium phosphate (DAP) and ammonium phosphate sulfate (APS) then.
Because the acid in the phosphoric acid ore deposit and the supersaturation property of impurity are to P
2O
5Enrichment step produce some side reactions, cause among the device of different steps of preparation phosphoric acid and/or on fouling.For example, silicofluoride is one of scale forming matter more general in the phosphoric acid production.It can be described through following equation:
Ca
5F(PO
4)
3+5H
2SO
4+5nH
2O→3H
3PO
4+5CaSO
4-nH
2O+HF
6HF+SiO
2→H
2SiF
6+2H
2O
In whole production process of phosphoric acid, can there be scale forming matter greater than other type of 12-15 kind, they become the significant challenge to industry.Equipment is every must to stop production to utilize high pressure water and/or mechanical to clear up fouling with physical method at a distance from several weeks usually.The economic impact of fouling associated problem is quite big, need be than the more effective technology that prevents fouling of the physical method of removing after the existing fouling in the industry.
Conceptive, what have two kinds of base types removes the method for fouling from production process of phosphoric acid, that is, and and physical method and chemical process.For physical method, there are several selections.Except above-mentioned machinery and method for washing, magnetic resolution (Wang, Chuhua; Benson, Robert F.; Martin, Dean F.Enhanced solubility of sodium fluorosilicate scale by magnetic treatment, Florida Scientist (1998), 61 (1), 17-25) and ultrasonic method (Pandey, A.D.; Mallick, K.K.; Pandey, P.C.; Varma; S.Prevention of scale deposition on heat exchanger surfaces by use of high intensity ultrasonic waves during concentration of wet process phosphoric acid; Fertiliser News (1983); 28 (6), 45-8) also as the physical method part.Adoptable another kind of method is in phosphoric acid production, to use the pipeline (referring to DE 3039187) of physics polishing.
As for chemical process, this method through adding reagent to change degree of supersaturation, perhaps causes deposition usually before filtration, perhaps stops the formation fouling to be implemented.This is a preferable methods, because its needs limited amount capital contribution and does not change the existing technology of phosphoric acid factory.Do not need a large amount of reagent yet, think that therefore environment and downstream are had minimum influence.
But the most of work on hands that solve scale problems in the phosphoric acid production equipment are based on the work that solves scale problems in the homogeneous solution-type reactor system.In feedwater, be used for some instances that fouling handles and be the for example multipolymer (EP0271035) of vinylformic acid and 2-acrylamido-2-methyl propane sulfonic acid (AMPS).It was reported that these polymkeric substance reduce the amount of the silica gel that adheres to the assay flask wall.Other system for example based on the monomer of polyamine, phosphonic acids and carboxylic acid and polymkeric substance also be illustrated in remove effectively in the boiler water system fouling (referring to, for example GB2424876, JP2002263690 and EP0677485).
Because the homogeneous solution-type reactor system is different from the environment that wet method prepares phosphoric acid greatly, this system is not provided for the optimal mode that phosphoric acid prepares process.The homogeneous solution-type reactor system has gentle condition usually, and wherein pH is 8-9, and the concentration of dissolved salt is low.By contrast, the environment that wet method prepares phosphoric acid generally includes violent condition, and wherein pH is low and solids content is high.In addition, the fouling in the phosphate equipment has more complicated component far away, comprises more than 15 kinds of known substances, for example Na
2SiF
6, K
2SiF
6, CaSiF
6.2H
2O, CaF
2, MgF
2, CaSO
4.2H
2O (gypsum), MgSiF
6.6H
2O, Mg
0.8Al
1.5F
6.XH
2O (wherein X is variable integer), MgH
2P
6O
7, CaSO
4, Al (PO
3)
3, NaK
2AlF
6, Ca
3(AlF
6)
2.4H
2O, MgNaAlF
6.2H
2O, Ca
4SO
4AlSiF
13.10H
2O (referring to for example, A.William Frazier, James R.Lehr, and Ewell F.Dillard, Environmental Science 8.Technology, 11,1007,1977).In addition, the fouling that different phosphate equipment experience is dissimilar, even in an equipment, the type of fouling has very big-difference between a position of technology and another position.Owing to form the complicacy of scale problems, constitute and split hair in the very big challenge of reagent that prevents and/or reduce the inhibition fouling of the fouling in the phosphate equipment.
For example, when typical 52% phosphoric acid of preparation, in boiler, apply the 60torr vacuum, make 85 ° of C phosphoric acid circulations, and under 130 ° of C, heat through heat exchanger.In this evaporative process, form some foulings at boiler or heat exchanger.But the fouling that forms at boiler possibly be different from the fouling that forms at heat exchanger.The fouling that slowly forms, the fouling that for example forms at heat exchanger mainly comprises hydrofluoaluminic acid magnesium; And the fouling that forms fast, the fouling that for example on pipeline, forms mainly comprises silicofluoric acid sodium salt or sylvite.
Yet, in industrial circle, few about the information that solves the phosphate equipment scale problems.Even for academic research, the result is rare.For example, the reagent that is used for suppressing in phosphoric acid production silicofluoride described in several pieces of articles.(referring to L.Yang, Zhang Y., Huang, Y.Chemical Industry and Engineering (China), (2002), and V 19 (1), and 1).The mixture of Chinese patent CN1762857 open phosphonic acids, polymkeric substance and sterilant can reduce the fouling that when wet method prepares phosphoric acid, forms effectively.USP 5,120,519 open high molecular weight polyacrylamides and ROHM can prevent that fouling from adhering to the surface of phosphate ore and phosphoric acid.But the purposes of these chemical of great majority is not recently, has been applied in and has controlled fouling in the water treatment system, and the mechanism of these reagent mainly is the dispersion agent effect according to them.
Therefore, need further improvement to can be used for preventing and/or reducing the compsn and the method for the fouling in the production process of phosphoric acid at present.Effectively prevent and/or reduce fouling make thus phosphoric acid production equipment can be under the situation of the scale removal that do not stop production compsn and the formula agent of the longer-term operation useful progress that is this area, and can in industry, obtain acceptance fast.
Summary of the invention
Have now found that, the water-soluble organic reagent of some prescription, in the various stages that wet method prepares phosphoric acid, prevent effectively and/or be suppressed among the production unit and/or on form multiple fouling.This type of formula agent prepares the PT of phosphoric acid through the time lengthening that reduces cleaning frequency/stopping production scale removal, thus the overall productivity of modifying device and equipment.
Therefore; In one aspect; The present invention is provided for preventing or reducing the method that wet method prepares at least a fouling in the phosphoric acid process; It is to add one or more water-soluble functionalized organic reagents through one or multistep step in this production technique, and said organic reagent is selected from: phosphonate derivative; Sulfonic acid or corresponding verivate; Carboxylic acid derivative; The phosphite derivative thing; Comprise first monomer that is selected from arbitrary aforementioned agents and the second monomeric multipolymer that is selected from suitable polymkeric substance; And the amount of this organic reagent is enough to prevent or reduce fouling; Condition is that said phosphonate derivative is not selected from: amino-three (methylene phosphonic acids) (ATMPA); 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (HEDPA); NSC 446-five (methylene phosphonic acid) (DTPMP); Quadrol methylene phosphonic acid (EDTMP); Hydroxyl ethyl phosphine acyl acetic acid (hydroxyl ethane phosphonothyl acetic acid) (HPAA); And phosphinylidyne butane-1,2, and the 4-tricarboxylic acid (phosphonobutane-1,2,4-tricarboxylic acid, PBTCA).In certain embodiments, said reagent also can with the known various mixed with polymers of those skilled in the art in the invention.
From following to various aspects of the present invention with obviously visible these and other purpose of the present invention of the detailed description of additional embodiment, feature and advantage.
Detailed Description Of The Invention
As above general introduction, the present invention be based in part on water-soluble functionalized organic reagent be used for preventing or reduce among the equipment of production process of phosphoric acid and/or on the purposes of fouling.
Definition
In the preceding text and the whole disclosure, use, provide following term to separate with the assistant.Only if definition in addition, the term that uses among all T.T.s, mark and other science or industry term or this paper has the implication of chemical field technician common sense.In some cases; In order to know and/or to be convenient to mention; Define term in this article, comprise definition like this in this article and should not be interpreted as necessarily that the expression and the definition of the term of this area common sense have essential distinction, except as otherwise noted with common sense implication.When in this paper and the claims of enclosing, using, only if context offers some clarification in addition, singulative comprises the indication thing of plural number.
In whole specification sheets, term and substituting group keep their definition.The comprehensive list of the abbreviation that organic chemist's (being those of ordinary skill in the art) is used is published in
Journal of Organic ChemistryIn the first phase of every volume.This tabulation typical case is that title is the table of " Standard List of Abbreviations ", includes in through quoting at this.
When using in this article, term " phosphonate derivative ", " sulfonic acid " and " carboxylic acid derivative " are meant the compound that in compound, contains phosphonic acids, sulfonic acid or carboxylic acid functional respectively.If phosphonic acids or sulfonic acid are present in the same compound with carboxylic acid, can depend on the circumstances compound called after phosphonate derivative or sulfonic acid.For example, for the application, sulfo-succinic acid is regarded as sulfonic acid.Similarly, for the application, phosphine acyl acetic acid and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid (PBTCA) is regarded as phosphonate derivative.
Term " multipolymer " is meant the polymkeric substance of being made up of two kinds or more kinds of different monomer when using in this article, wherein said monomer randomly or with Tumor-necrosis factor glycoproteins or block or as the side chain form of main chain links to each other.Therefore, for example, the phosphonate derivative multipolymer is meant to comprise phosphonate derivative monomer (i.e. first monomer) multipolymer random with one or more other monomers (i.e. second monomer) or that link to each other with Tumor-necrosis factor glycoproteins.Those of ordinary skills understand, and known various different monomers can be used as second monomer and form multipolymer of the present invention.Similarly, form sulfonic acid copolymer or sulfonic acid multipolymer etc.
When using in this article, as understood by one of ordinary skill in the art, term " reagent " is intended to comprise the salt and the solvolyte of this reagent, and any stereoisomer form, perhaps the mixture of the arbitrary proportion of any this type of form of this reagent.
When reagent of the present invention is alkaline, can prepare salt by the acceptable nontoxicity acid that comprises mineral acid and organic acid.For reagent of the present invention, suitable acid-adducting salt comprises acetate, benzene sulfonate, benzoate, camsilate, Citrate trianion, esilate, fumarate, gluconate, glutaminate, hydrobromate, hydrochloride, isethionate, lactic acid salt, PHENRAMINE MALEATE, malate, tonsilla hydrochlorate, mesylate, mucate, nitrate salt, embonate, pantothenate, phosphoric acid salt, SUMATRIPTAN SUCCINATE, vitriol, tartrate, tosilate etc.When said reagent comprises acid side-chain; For reagent of the present invention; The acceptable alkali adduct that is fit to comprises the metal-salt of being processed by aluminium, calcium, lithium, magnesium, potassium, sodium and zinc, perhaps by Methionin, N, and the organic salt that N'-dibenzyl-ethylenediamin, diethylolamine and quadrol make.
All numerical value that in specification sheets and claims, are used for expressing the amount, reaction conditions etc. of component are interpreted as in all situations, being modified by term " about ".Therefore, only if explanation on the contrary, the character of the expectation that specification sheets and the numerical parameter described in claims of enclosing can be attempted according to the present invention to obtain and the approximation that changes.In addition, each numerical parameter should be understood with reference to significant figure and the conventional method that rounds.
In the repetition flash distillation/cooling/enrichment step of production process of phosphoric acid, on heat exchanger, vaporizer, thickener and pipeline, form fouling from production process of phosphoric acid.Setting causes that the system of fouling to simulate this process, wherein is immersed in pipe in the hot phosphoric acid solution through stainless steel tube supply heat or cold water simultaneously.Thermograde and free-pouring solid cause on the outside of pipe, forming fouling.This system is the basis of the corresponding embodiment that provides of this paper, also use under equivalent environment control flask and sample flask relatively.Method
In first aspect; The present invention provides and prevents or reduce the method that wet method prepares at least a scale forming matter in the phosphoric acid process; Said method comprises: one or multistep step in production process of phosphoric acid are added water-soluble functionalized organic reagent, and said organic reagent is selected from one or more in the following material: phosphonate derivative; Sulfonic acid or corresponding verivate; Carboxylic acid derivative; The phosphite derivative thing; Comprise first monomer that is selected from arbitrary aforementioned agents and the second monomeric multipolymer that is selected from any suitable polymkeric substance; And the amount of organic reagent is enough to prevent or reduce fouling; Condition is that said phosphonate derivative is not selected from: amino-three (methylene phosphonic acids) (ATMPA); 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid (HEDPA); NSC 446-five (methylene phosphonic acid) (DTPMP); Quadrol methylene phosphonic acid (EDTMP); Hydroxyl ethyl phosphine acyl acetic acid (HPAA); And phosphinylidyne butane-1,2,4-tricarboxylic acid (PBTCA).
In one embodiment, in production process of phosphoric acid, be prevented from or the scale forming matter that suppresses includes but not limited in the following material one or more: Si
2F
6Na
2SiF
6K
2SiF
6CaSiF
6/ 2H
2O; CaF
2MgF
2CaSO
4/ 2H
2O; MgSiF
6/ 6H
2O; Mg
0.8Al
1.5F
6/ X H
2O (wherein X is the integer of 2-20); MgH
2P
6O
7CaSO
4Al (PO
3)
3NaK
2AlF
6Ca
3(AlF
6)
2/ 4H
2O; MgNaAlF
6/ 2H
2O; And Ca
4SO
4AlSiF
13/ 10H
2O.
In some embodiments, said water-soluble functionalized organic reagent can add at the arbitrary steps of production process of phosphoric acid, and said step is well known to those skilled in the art.In certain embodiments, for example, said interpolation step can occur in the grinding steps, acidolysis step, filtration step, purification step (clarifying step) of production process of phosphoric acid and concentrate/one or multistep step in evaporation step in.In one embodiment, said interpolation step occurs in after the acidolysis step of production process of phosphoric acid.In another embodiment, said interpolation step occurs in concentrating/evaporation step of said technology.
Can be with various forms, for example, single phase, multistage, successively, reverse order, simultaneously or the form of its various combinations mix said reagent.For example, in one embodiment, add said reagent, mix with phosphoric acid then to form premixture.In another embodiment, through respectively the component of said reagent being mixed the on-the-spot said reagent that forms with phosphoric acid.Various interpolation patterns are feasible.
The said reagent that comprises liquid (for example water, oil and/or alcohol) can be prepared with the whole bag of tricks; For example; Can solid reagent be suspended (for example colloidal suspension liquid), be dispersed in the liquid and/or become pulp slurry, and/or can said reagent be suspended, be scattered in the liquid, become pulp slurry and/or be dissolved in the liquid.In one embodiment, can said reagent be added into phosphoric acid solution dividually.In another embodiment, with said reagent pre-mixing, be added into phosphoric acid solution together.
In one embodiment, the concentration of said water-soluble functionalized organic reagent is 10-1000g/ ton phosphoric acid (for example, the phosphoric acid of 10g/ ton, 20g/ ton, 30g/ ton, 40g/ ton, 50g/ ton, 60g/ ton, 70g/ ton, 80g/ ton, 90g/ ton, 100g/ ton, 110g/ ton, 120g/ ton, 130g/ ton, 140g/ ton, 150g/ ton, 160g/ ton, 170g/ ton, 180g/ ton, 190g/ ton, 200g/ ton, 210g/ ton, 220g/ ton, 230g/ ton, 240g/ ton, 250g/ ton, 260g/ ton, 270g/ ton, 280g/ ton, 290g/ ton, 300g/ ton, 310g/ ton, 320g/ ton, 330g/ ton, 340g/ ton, 350g/ ton, 360g/ ton, 370g/ ton, 380g/ ton, 390g/ ton, 400g/ ton, 410g/ ton, 420g/ ton, 430g/ ton, 440g/ ton, 450g/ ton, 460g/ ton, 470g/ ton, 480g/ ton, 490g/ ton, 500g/ ton, 510g/ ton, 520g/ ton, 530g/ ton, 540g/ ton, 550g/ ton, 560g/ ton, 570g/ ton, 580g/ ton, 590g/ ton, 600g/ ton, 610g/ ton, 620g/ ton, 630g/ ton, 640g/ ton, 650g/ ton, 660g/ ton, 670g/ ton, 680g/ ton, 690g/ ton, 700g/ ton, 710g/ ton, 720g/ ton, 730g/ ton, 740g/ ton, 750g/ ton, 760g/ ton, 770g/ ton, 780g/ ton, 790g/ ton, 800g/ ton, 810g/ ton, 820g/ ton, 830g/ ton, 840g/ ton, 850g/ ton, 860g/ ton, 870g/ ton, 880g/ ton, 890g/ ton, 900g/ ton, 910g/ ton, 920g/ ton, 930g/ ton, 940g/ ton, 950g/ ton, 960g/ ton, 970g/ ton, 980g/ ton, 990g/ ton, 1000g/ ton).In another embodiment, the concentration of said water-soluble functionalized organic reagent is 50-300g/ ton phosphoric acid.In a preferred embodiment, the concentration of said water-soluble functionalized organic reagent is 100g/ ton phosphoric acid.
In many cases, can form the substance change treatment time of speed and/or fouling according to fouling.For example, if in 30 minutes handle, form fouling, then the entire treatment time can be just in time 1 hour.If in 4 hours handle, do not form fouling, then the entire treatment time can be above 1 day.Those of ordinary skills can confirm the proper process time through conventional means.
In one embodiment, depend on the amount and the type of fouling, the fouling that prevention or minimizing formed from 10 days to 180 days production process of phosphoric acid.
The pH of phosphoric acid, though unjustified, the changing value after adding reagent treatment should not reach 1.Before method of the present invention began, the preferred pH of phosphoric acid should be 1-5.Under the pH of phosphoric acid, be reduced in 1 the situation, it can be adjusted through sodium hydroxide or soda ash light.In the pH of phosphoric acid was higher than 5 situation, it can be adjusted through adding sulfuric acid or phosphoric acid.
In one embodiment, said water-soluble functionalized organic reagent is to be selected from phenyl-phosphonic acid, phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) (HEMPA) and the phosphonate derivative of their mixture.
In another embodiment, said water-soluble functionalized organic reagent is to be selected from following sulfonic acid: sulfo-succinic acid; 5-sulphosalicylic acid hydrate; The 4-sulfosalicylic phthalate; N-(1,1-dimethyl--2-hydroxyethyl)-3-amino-2-hydroxy-propanesulfonic acid (AMPSO); 3-amino-4-hydroxy Phenylsulfonic acid; 1-dodecane sulfonic acid sodium salt; Vinylformic acid (3-sulfonic acid third) ester sylvite; 4-hydroxy benzenesulfonic acid solution; 4,5-dihydroxy naphthlene-2,7-disulfonic acid disodium salt; 2,5-dihydroxy benzenes sulfonic acid sylvite (hydroquinonesulfonic acid potassium salt); And their mixture.
In another embodiment, said water-soluble functionalized organic reagent is to be selected from 3,4-dihydroxyl phenylpropionic acid; 3, the 4-resorcylic acid; Gallic acid; Coffic acid; Tartrate; And the carboxylic acid derivative of their mixture.
In another embodiment; Said water-soluble functionalized organic reagent is to comprise phosphonate derivative, sulfonic acid or corresponding verivate, carboxylic acid derivative or phosphite derivative thing as first monomer and the second monomeric multipolymer; Second monomer is selected from any suitable polymkeric substance, includes but not limited to: polymine-epoxy-hydroxy succinic acid ester; CYANAMER P-
(can derive from Cytec Industries Inc.; Woodland Park, NJ); CYANAMER P-
(can derive from Cytec Industries Inc.; Woodland Park, NJ);
C573; C587 (can derive from Cytec Industries Inc.; Woodland Park, NJ); Gather (4-styrene sulfonic acid); The phosphino-polycarboxylic acid; Acrylic acid/esters/sulphonate multipolymer; ROHM (PAA); ZX-I (PAAS); P-methoxy-phenyl maleinamic acid (MPMA); Maleic anhydride XPA (MA-AA); AA-MA-acrylamido-methyl-propanesulfonic acid ester polymer (AMPS) Hypophosporous Acid, 50 (hypophosphorous acid) quadripolymer; The AA-AMPS multipolymer; AA-Yodo Sol GH 28 T-225; And vinylformic acid-2-methyl propane sulfonic acid XPA; And their mixture.In certain embodiments, any said reagent and/or multipolymer also can mix with the polymkeric substance (for example those described in this paper) that is fit to.
Preferred reagent used in the method for the present invention comprises, for example, and phosphine acyl acetic acid; Tannic acid phosphorous acid ester (tannic phosphite); Hydroxyethylamino-two (methylene phosphonic acid) (HEMPA); Sulfonic acid; Sulfo-succinic acid; 5-sulphosalicylic acid hydrate; N-(1,1-dimethyl--2-hydroxyethyl)-3-amino-2-hydroxy-propanesulfonic acid (AMPSO); Vinylformic acid (3-sulfonic acid third) ester sylvite; 1-dodecane sulfonic acid sodium salt; 4-hydroxy benzenesulfonic acid solution; 4,5 ,-dihydroxy naphthlene-2,7-disulfonic acid disodium salt; 3, the 4-dihydroxyphenyl acetic acid; 3,4-dihydroxyl phenylpropionic acid; 3, the 4-resorcylic acid; Tartrate; Polymine-epoxy-hydroxy succinic acid ester; And in their mixture one or more.
In certain embodiments, said method also can comprise with flocculation agent make phosphoric acid flocculation, with digestion agent lixiviate phosphoric acid, make one or multistep step in phosphoric acid precipitates and the filtration phosphoric acid with precipitation agent.The used typical reagent of these additional steps is that those of ordinary skills are known.
Other embodiment
Prevent 1, or reduce the method that wet method prepares at least a scale forming matter in the process phosphoric acid that said method comprises:
Step in production process of phosphoric acid or multistep step are added with the amount that is enough to prevent or reduce said fouling and are selected from one or more following reagent:
I) phosphonate derivative;
Ii) sulfonic acid or verivate accordingly;
Iii) carboxylic acid derivative;
Iv) phosphite derivative thing; With
V) comprise second monomer and be selected from (the i) – first monomeric multipolymer (iv);
Condition is; Said phosphonate derivative is not selected from: amino-three (methylene phosphonic acids) (ATMPA), 1-hydroxy ethylene-1; 1-di 2 ethylhexyl phosphonic acid (HEDPA), NSC 446-five (methylene phosphonic acid) (DTPMP), quadrol methylene phosphonic acid (EDTMP), hydroxyl ethyl phosphine acyl acetic acid (HPAA) and phosphinylidyne butane-1; 2,4-tricarboxylic acid (PBTCA).
2, the method for embodiment 1, wherein the kind of phosphoric acid fouling is selected from one or more in following: Si
2F
6, Na
2SiF
6, K
2SiF
6, CaSiF
6/ 2H
2O, CaF
2, MgF
2, CaSO
4/ 2H
2O, MgSiF
6/ 6H
2O, Mg
0.8Al
1.5F
6/ X H
2O, MgH
2P
6O
7, CaSO
4, Al (PO
3)
3, NaK
2AlF
6, Ca
3(AlF
6)
2/ 4H
2O, MgNaAlF
6/ 2H
2O and Ca
4SO
4AlSiF
13/ 10H
2O, wherein X is the integer of 2-10.
3, the method for each in the previous embodiments, wherein said interpolation step occur in the grinding steps, acidolysis step, filtration step, purification step of production process of phosphoric acid and concentrate/evaporation step in a step or a multistep.
4, the method for embodiment 3, wherein said interpolation step occurs in after the acidolysis step of said production process of phosphoric acid.
5, the method for embodiment 3, wherein said interpolation step occur in concentrating/evaporation step of said production process of phosphoric acid.
6, the method for each in the previous embodiments, wherein said interpolation step with single phase, multistage, continuously, opposite order, side by side or their combination implement.
7, the method for each in the previous embodiments, wherein said reagent be added directly to phosphoric acid or with the solvent pre-mixing that is selected from water, oil, alcohol and their mixture.
8, the method for embodiment 7, wherein said reagent and solvent pre-mixing and provide with the form of colloidal suspension liquid, dispersion-s, slurry perhaps are dissolved in said solvent.
9, the method for each in the previous embodiments, wherein said reagent are to be selected from phenyl-phosphonic acid, phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) (HEMPA) and the phosphonate derivative of their mixture.
10, the method for each among the embodiment 1-8; Wherein said reagent is sulfonic acid; It is selected from: sulfo-succinic acid, 5-sulphosalicylic acid hydrate, 4-sulfosalicylic phthalate, N-(1; 1-dimethyl--2-hydroxyethyl)-3-amino-2-hydroxy-propanesulfonic acid (AMPSO), 3-amino-4-hydroxy Phenylsulfonic acid, 1-dodecane sulfonic acid sodium salt, vinylformic acid (3-sulfonic acid third) ester sylvite, 4-hydroxy benzenesulfonic acid solution, 4; 5-dihydroxy naphthlene-2,7-disulfonic acid disodium salt, 2,5-dihydroxy benzenes sulfonic acid sylvite and their mixture.
11, the method for each among the embodiment 1-8, wherein said reagent is to be selected from 3,4-dihydroxyphenyl acetic acid, 3,4-dihydroxyl phenylpropionic acid, 3, the carboxylic acid of 4-resorcylic acid, gallic acid, coffic acid, tartrate and their mixture.
12, the method for each among the embodiment 1-8; Wherein said reagent is multipolymer, and wherein said second monomer is selected from: polymine-epoxy-hydroxy succinic acid ester, CYANAMERP-
CYANAMER P-
gather (4-styrene sulfonic acid), phosphino-polycarboxylic acid, acrylic acid/esters/sulphonate, ROHM (PAA), ZX-I (PAAS), p-methoxy-phenyl maleinamic acid (MPMA), maleic anhydride XPA (MA-AA), AA-MA-acrylamido-methyl-propanesulfonic acid ester polymer (AMPS) Hypophosporous Acid, 50 quadripolymer, AA-AMPS multipolymer, AA-Yodo Sol GH 28 T-225 and vinylformic acid-2-methyl propane sulfonic acid XPA and their mixture.
13, the method for each among the embodiment 1-12; Wherein said reagent is selected from: phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) (HEMPA), tannic acid phosphorous acid ester, sulfonic acid, sulfo-succinic acid, 5-sulphosalicylic acid hydrate, N-(1; 1-dimethyl--2-hydroxyethyl)-3-amino-2-hydroxy-propanesulfonic acid (AMPSO), vinylformic acid (3-sulfonic acid third) ester sylvite (3-sulfopropyl acrylate potassium salt), 1-dodecane sulfonic acid sodium salt, 4-hydroxy benzenesulfonic acid solution, 4; 5-dihydroxy naphthlene-2; 7-disulfonic acid disodium salt, 3; 4-dihydroxyphenyl acetic acid, 3,4-dihydroxyl phenylpropionic acid, 3,4-resorcylic acid, tartrate, polymine-epoxy-hydroxy succinic acid ester and their mixture.
14, the method for each in the previous embodiments, the concentration of wherein said reagent are 10-1000g/ ton phosphoric acid.
15, the method for embodiment 14, the concentration of wherein said reagent are 50-300g/ ton phosphoric acid.
16, the method for embodiment 15, the concentration of wherein said reagent are 100g/ ton phosphoric acid.
17, the method for each in the previous embodiments wherein prevented or reduced said fouling in lasting 10-180 days.
18, the method for each in the previous embodiments, it also comprises from the phosphoric acid of gained removes the metals ion that causes fouling.
19, the method for embodiment 18, wherein said removing step is implemented through with one or more flocculation agents phosphoric acid being flocculated.
20, the method for each among the embodiment 18-19, it also comprises with one or more digestion agent lixiviate phosphoric acid.
21, the method for each among the embodiment 18-20, it also comprises with one or more precipitation agents handles phosphoric acid.
22, the method for each among the embodiment 18-21, it also comprises filtration phosphoric acid.
Prevent 23, or reduce the method that wet method prepares at least a scale forming matter in the process phosphoric acid that said method comprises:
Add with the amount that is enough to prevent or reduce said fouling in step of said production process of phosphoric acid or multistep step and to be selected from one or more following reagent:
I) phosphonate derivative is selected from phenyl-phosphonic acid, phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) (HEMPA) and their mixture;
Ii) sulfonic acid or derivatives thereof;
Iii) carboxylic acid derivative;
Iv) phosphite derivative thing; With
V) comprise second monomer and the first monomeric multipolymer that is selected from (i)-(iv).
Prevent 24, or reduce the method that wet method prepares at least a scale forming matter in the process phosphoric acid that said method comprises:
Step in said production process of phosphoric acid or multistep step are added with the amount that is enough to prevent or reduce said fouling and are selected from one or more following reagent:
I) sulfonic acid or corresponding verivate;
Ii) carboxylic acid derivative;
Iii) phosphite derivative thing; With
Iv) comprise second monomer and be selected from (the i) – first monomeric multipolymer (iii).
Embodiment
Embodiment
Provide following examples further to understand embodiment of the present invention to help those skilled in the art.These embodiment are intended to explanation, and should not be construed as the scope of the restriction embodiment of the present invention or the claim of enclosing.
The phosphoric acid solution that is used for reagent test is from phosphoric acid factory (Agrium for example, Inc.Canada (A of factory); Prayon, Inc., Georgia (P of factory); With The Mosaic Company, Florida (M of factory)) with 28%, 42%, 52% or 69%P
2O
5Obtain.ICP and XRD analysis show that the significant difference of raw phosphoric acid is their metal component, and this causes reasonably being difficult to form fouling in the time sometimes.Therefore, cause that with salt fouling forms sometimes.In some cases, add 0.1%-10%NaCl, KCl or MgCl
2Salt forms to cause specific fouling.These crude samples comprise 28% and 69% P
2O
5(from the A of factory), 30% and 54%P
2O
5(from the P of factory) and 30%P
2O
5(from the M of factory).These sample former states are used, and perhaps are diluted to suitable concentration use through adding water, perhaps are adjusted to more spissated solution use through adding 86% commercial grade phosphoric acid.In some cases, also add 0.1%-3%NaCl, KCl or MgCl
2Salt forms in test process, to cause specific fouling.
Cause fouling with following mode:
Step 1: acid preparation-in this step, obtain raw phosphoric acid from phosphoric acid factory, suitably handle (former state, dilution concentrate or add the salt as the fouling initiator), continue 0.5-2 hour, place chuck beaker (60 ° of C-80 ° of C) then.
Step 2: test set is installed with chemical and is added-after processing, the functionalized organic reagent of suitable dosage is added in the phosphoric acid, utilizes the stirring rod stirring to heat at 60 ° of C-90 ° of C with water recirculator simultaneously.The plastics tubing of 316L stainless steel tube, lid and water-in and water outlet is installed in each beaker simultaneously.Perhaps, can use carbon tube or 904L stainless steel tube, and the temperature of pipe can be 110 ° of C-130 ° of C.
Step 3: fouling Xing Cheng – can add it if use the functionalized organic reagent prevent or reduce fouling, then adjusts (additive uses with the solution form of the potent agent that comprises 1%-10% usually) immediately.This solution is added in the phosphoric acid that is processed in chuck beaker, 60 ° of C-80 ° of C heating and stirred 30 minutes, open pipe waster section (waster) then and kept 2-12 hour in this temperature.Carry out 2-9 so test (beaker) simultaneously.When EOT, fully wash tube and in baking oven (80 ° of C) dry 1-2 hour.
Step 4: weighing is also analyzed Jie Gou – and is observed the considerable fouling of formation on steel pipe.The weightening finish of steel pipe is measuring of amount of scale buildup.The weight of the fouling that forms is to account for the percentage expression that the blank (promptly not using reagent) that belongs to same test group part goes up the weight in average that forms.Similarly, also to be that antiscale is active measure the total amount of fouling, and this can test the percentage expression of the total amount that forms in (belonging to identical test group part) in vain with duty.Also obtain metals ion and component information through ICP and XRD analysis fouling.
This testing method is preferred, because other testing method is collected fouling and insolubles, but this insolubles can unrestricted flow in the acid stream of actual factory, so fouling is increased not significant contribution.In this test, on the outside surface of stainless steel tube, collect fouling.Weighing tube, and relatively calculate fouling with pipe without agent treated and change.Usually in de-ionized (" DI ") water, prepare reagent, the ultimate density with 3% is used for test.Unless otherwise indicated, the concentration of reagent in test soln is 2000ppm to the maximum.
Take every caution against error guarantee all parameters (such as but not limited to; Mixing velocity, pipe temperature, jacket temperature, tube-surface character, buried pipe volume, stirring rod size and acid matter) closer to each other, thus have meaning with result that the fouling of control sample comparison suppresses.
Embodiment 1
4 chuck beakers are placed and are fixed on the aluminium dish (on four jiaos of hot-plate) of the DI-water that is full of with clip.With respect to current, with the parallel connection of beaker from the heating cycle device.Thorough mixing phosphoric acid (synthetic or 28% thick factory acid sample) is divided equally in 4 beakers (450-700g) then.Mix beaker with stirring rod simultaneously with identical speed.Start hot-plate with the temperature of heating in water bath to about 90 ° of C.Behind the mixed stability in each beaker, start the power supply of heating cycle device.When the temperature reading of circulator is about 50-60 ° of C, reagent is added to each beaker (normally three in them remain as contrast).
4 U-shaped pipes of being weighed in advance that will be connected to tap water then are immersed in the corresponding beaker.When circulator shows about 75 ° of C, open tap water with cooling U-shaped pipe.Coming from the terminal tap water temperature of last U-shaped pipe is about 25 ° of C.Continue the mixing in each beaker, suspend careful monitoring once in a while.Monitor all tap water continually and add hot water and be connected and check possible leakage and cutout.
Handled (perhaps until forming the visible fouling on the pipe) at 2 hours after, close the heating of chuck and the water coolant of pipe, and stop to stir the heating with hot-plate.Off-tube connects, and in beaker, cleans to remove phosphoric acid remaining on the pipe with 500ml DI water.To manage then in baking oven under 80 ° of C dry 1 hour; Be cooled to room temperature; Weighing then they, draw the fouling weight on the pipe according to following equation: fouling reduces (increase) %=100x (the fouling weight when the fouling Chong Liang – when reagent is arranged does not have reagent)/(the fouling weight when not having reagent).When needing, carry out icp analysis and XRD analysis.
After fouling research finishes, remove beaker with attached clip, used acid solution is poured in the waste vessel.Clean beaker is given back to their original position and is used for lower whorl test.The cleaning stainless steel tube, oven drying is weighed, and then is used for the lower whorl test.
Various functionalized organic reagents prevent or the result that reduces fouling is shown among the following table A-D:
Table A. use the test result of single compound phosphonate derivative reagent
Table B. uses the test result of single compound sulfonic acid reagent
Table C. uses the test result of single compound carboxylic acid derivative reagent
Table D. use mixture or multipolymer are as the test result of reagent
Embodiment 2
Test conditions is similar with embodiment 1, but phosphoric acid concentration increases to 52%.Form to increase fouling in order to increase temperature head, perhaps test with 35 ° of C pipe temperature and 70 ° of C acid temperature with 55 ° of C pipe temperature and 80 ° of C acid temperature.In all tests, stir with 240rpm-300rpm, use 1kg acid and 100ppm (3% solution of 3g) reagent.The time length of test is 2-6 hour.
The result is shown among the following table E:
Table E is at 52%P
2O
5The test result of all ingredients
The typical process of the test of the polyethylene imine based succinate of hydroxyl is following: in accordance with known methods Synthetic 2 g suitable-the epoxy succinic acid disodium salt, it is mixed with 50% polymine (PEI) of 8.3g, heating is (pure or at CH
3Among the CN), and under 80 ° of C, stir 4hr.After the cooling, handle viscous liquid, thereafter its sclerosis with hexane.It is filtered, dry with weigh.Solid is soluble in water, be used for the concentration adjustment.The reagent test result is summarized among the table F, with respect to blank (wherein not using reagent), with the per-cent report of the fouling that forms.
Table F. uses the test result of the polyethylene imine based succinate of hydroxyl
Various patents and/or scientific literature in whole the application, have been quoted.Incorporate the whole open of these publications at this into through quoting, as said open consistent with the present invention and meet permission like this through the degree of quoting all authorities of including on written description in this article.In view of above description and embodiment, those of ordinary skill in the art can implement said open under suitable test.
Though the description of front shows, describe and point out basic new feature of the present invention, should be understood that without departing from the scope of the invention, those skilled in the art can carry out various omissions, substitute and change described method.Therefore, scope of the present invention should be not limited to the argumentation of front, and should be limited the claims of enclosing.
Claims (20)
1. prevent or reduce the method that wet method prepares at least a scale forming matter in the process phosphoric acid that said method comprises:
Step in production process of phosphoric acid or multistep step are added with the amount that is enough to prevent or reduce said fouling and are selected from one or more following reagent:
I) phosphonate derivative;
Ii) sulfonic acid or verivate accordingly;
Iii) carboxylic acid derivative;
Iv) phosphite derivative thing; With
V) comprise second monomer and be selected from (the i) – first monomeric multipolymer (iv);
Condition is; Said phosphonate derivative is not selected from: amino-three (methylene phosphonic acids) (ATMPA), 1-hydroxy ethylene-1; 1-di 2 ethylhexyl phosphonic acid (HEDPA), NSC 446-five (methylene phosphonic acid) (DTPMP), quadrol methylene phosphonic acid (EDTMP), hydroxyl ethyl phosphine acyl acetic acid (HPAA) and phosphinylidyne butane-1; 2,4-tricarboxylic acid (PBTCA).
2. the process of claim 1 wherein that the kind of phosphoric acid scale forming matter is selected from one or more in following: Si
2F
6, Na
2SiF
6, K
2SiF
6, CaSiF
6/ 2H
2O, CaF
2, MgF
2, CaSO
4/ 2H
2O, MgSiF
6/ 6H
2O, Mg
0.8Al
1.5F
6/ X H
2O, MgH
2P
6O
7, CaSO
4, Al (PO
3)
3, NaK
2AlF
6, Ca
3(AlF
6)
2/ 4H
2O, MgNaAlF
6/ 2H
2O and Ca
4SO
4AlSiF
13/ 10H
2O, wherein X is the integer of 2-10.
3. each method in the aforementioned claim, wherein said interpolation step occur in the grinding steps, acidolysis step, filtration step, purification step of production process of phosphoric acid and concentrate/evaporation step in a step or a multistep.
4. each method in the aforementioned claim, wherein said interpolation step with single phase, multistage, continuously, opposite order, side by side or their combination implement.
5. each method in the aforementioned claim, wherein said reagent be added directly to phosphoric acid or with the solvent pre-mixing that is selected from water, oil, alcohol and their mixture.
6. each method in the aforementioned claim, wherein said phosphonate derivative is selected from: phenyl-phosphonic acid, phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) are (HEMPA) and their mixture.
7. each method among the claim 1-5; Wherein said sulfonic acid is selected from: sulfo-succinic acid, 5-sulphosalicylic acid hydrate, 4-sulfosalicylic phthalate, N-(1; 1-dimethyl--2-hydroxyethyl)-3-amino-2-hydroxy-propanesulfonic acid (AMPSO), 3-amino-4-hydroxy Phenylsulfonic acid, 1-dodecane sulfonic acid sodium salt, vinylformic acid (3-sulfonic acid third) ester sylvite, 4-hydroxy benzenesulfonic acid solution, 4; 5-dihydroxy naphthlene-2; 7-disulfonic acid disodium salt, 2,5-dihydroxy benzenes sulfonic acid sylvite and their mixture.
8. each method among the claim 1-5, wherein said carboxylic acid is selected from: 3,4-dihydroxyphenyl acetic acid, 3,4-dihydroxyl phenylpropionic acid, 3,4-resorcylic acid, gallic acid, coffic acid, tartrate and their mixture.
9. each method among the claim 1-5; Wherein said reagent is multipolymer, and wherein said second monomer is selected from: polymine-epoxy-hydroxy succinic acid ester, CYANAMERP-
CYANAMER P-
gather (4-styrene sulfonic acid), phosphino-polycarboxylic acid, acrylic acid/esters/sulphonate, ROHM (PAA), ZX-I (PAAS), p-methoxy-phenyl maleinamic acid (MPMA), maleic anhydride XPA (MA-AA), AA-MA-acrylamido-methyl-propanesulfonic acid ester polymer (AMPS) Hypophosporous Acid, 50 quadripolymer, AA-AMPS multipolymer, AA-Yodo Sol GH 28 T-225 and vinylformic acid-2-methyl propane sulfonic acid XPA and their mixture.
10. each method among the claim 1-9; Wherein said reagent is selected from: phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) (HEMPA), tannic acid phosphorous acid ester, sulfonic acid, sulfo-succinic acid, 5-sulphosalicylic acid hydrate, N-(1; 1-dimethyl--2-hydroxyethyl)-3-amino-2-hydroxy-propanesulfonic acid (AMPSO), vinylformic acid (3-sulfonic acid third) ester sylvite, 1-dodecane sulfonic acid sodium salt, 4-hydroxy benzenesulfonic acid solution, 4; 5-dihydroxy naphthlene-2; 7-disulfonic acid disodium salt, 3; 4-dihydroxyphenyl acetic acid, 3,4-dihydroxyl phenylpropionic acid, 3,4-resorcylic acid, tartrate, polymine-epoxy-hydroxy succinic acid ester and their mixture.
11. each method in the aforementioned claim, the concentration of wherein said reagent are 10-1000g/ ton phosphoric acid.
12. the method for claim 11, the concentration of wherein said reagent are 100g/ ton phosphoric acid.
13. each method in the aforementioned claim wherein prevented or reduced said fouling in lasting 10-180 days.
14. the method for each in the aforementioned claim, it also comprises from the phosphoric acid of gained removes the metals ion that causes fouling.
15. the method for claim 14, wherein said removing step is implemented through with one or more flocculation agents phosphoric acid being flocculated.
16. each method among the claim 14-15, it also comprises with one or more digestion agent lixiviate phosphoric acid.
17. each method among the claim 14-16, it also comprises with one or more precipitation agents handles phosphoric acid.
18. each method among the claim 14-17, it also comprises filtration phosphoric acid.
19. prevent or reduce the method that wet method prepares at least a scale forming matter in the process phosphoric acid that said method comprises:
Add with the amount that is enough to prevent or reduce said fouling in step of production process of phosphoric acid or multistep step and to be selected from one or more following reagent:
I) phosphonate derivative is selected from phenyl-phosphonic acid, phosphine acyl acetic acid, hydroxyethylamino-two (methylene phosphonic acid) (HEMPA) and their mixture;
Ii) sulfonic acid or derivatives thereof;
Iii) carboxylic acid derivative;
Iv) phosphite derivative thing; With
V) comprise second monomer and be selected from (the i) – first monomeric multipolymer (iv).
20. prevent or reduce the method that wet method prepares at least a scale forming matter in the process phosphoric acid that said method comprises:
Step in production process of phosphoric acid or multistep step are added with the amount that is enough to prevent or reduce said fouling and are selected from one or more following reagent:
I) sulfonic acid or corresponding verivate;
Ii) carboxylic acid derivative;
Iii) phosphite derivative thing; With
Iv) comprise second monomer and be selected from (the i) – first monomeric multipolymer (iii).
Applications Claiming Priority (3)
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|---|---|---|---|
| US24571309P | 2009-09-25 | 2009-09-25 | |
| US61/245,713 | 2009-09-25 | ||
| PCT/US2010/050086 WO2011038167A1 (en) | 2009-09-25 | 2010-09-24 | Preventing or reducing scale in wet-process phosphoric acid production |
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| EP (1) | EP2480496A1 (en) |
| CN (1) | CN102712476B (en) |
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| AR (1) | AR078448A1 (en) |
| AU (1) | AU2010298172B2 (en) |
| BR (1) | BR112012006675A2 (en) |
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| IL (1) | IL218757A (en) |
| JO (1) | JO3035B1 (en) |
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| TN (1) | TN2012000121A1 (en) |
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| CN107635917A (en) * | 2015-02-11 | 2018-01-26 | 塞特工业公司 | The amine of the modification useful as the scale inhibitor in Wet-process Phosphoric Acid Production |
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| 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 |
| US8900539B2 (en) | 2011-03-22 | 2014-12-02 | Cytec Technology Corp. | Preventing or reducing scale in wet-process phosphoric acid production |
| MA35044B1 (en) * | 2011-03-22 | 2014-04-03 | Cytec Tech Corp | PREVENTING OR REDUCING SCALE FORMATION IN THE PRODUCTION OF PHOSPHORIC ACID IN A WET PROCESS |
| CN110396149B (en) | 2014-02-11 | 2023-09-05 | 塞特工业公司 | 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 |
| CN115571863B (en) * | 2022-10-08 | 2024-02-09 | 广东邦普循环科技有限公司 | Wet phosphoric acid scale-dissolving agent and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| AP2012006168A0 (en) | 2012-04-30 |
| AU2010298172A1 (en) | 2012-04-19 |
| TN2012000121A1 (en) | 2013-09-19 |
| EA201270464A1 (en) | 2012-10-30 |
| EP2480496A1 (en) | 2012-08-01 |
| MA33797B1 (en) | 2012-12-03 |
| CA2775344A1 (en) | 2011-03-31 |
| BR112012006675A2 (en) | 2016-05-10 |
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| CN102712476B (en) | 2019-03-12 |
| PE20121419A1 (en) | 2012-10-17 |
| IL218757A0 (en) | 2012-06-28 |
| AR078448A1 (en) | 2011-11-09 |
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