CN100431985C - Scale inhibitor for wet method phosphoric acid manufacture - Google Patents

Scale inhibitor for wet method phosphoric acid manufacture Download PDF

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Publication number
CN100431985C
CN100431985C CNB2005102005053A CN200510200505A CN100431985C CN 100431985 C CN100431985 C CN 100431985C CN B2005102005053 A CNB2005102005053 A CN B2005102005053A CN 200510200505 A CN200510200505 A CN 200510200505A CN 100431985 C CN100431985 C CN 100431985C
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acid
phosphoric acid
scale
wet method
agent
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CN1762857A (en
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刘天暘
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation
    • C23F15/005—Inhibiting incrustation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • 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
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B15/00—Organic phosphatic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The present invention discloses a scale preventing agent for phosphoric acid manufacture by a wet method, which relates to the technical field of fertilizer manufacture. The scale preventing agent is formed by combining an organic phosphine scale preventing corrosion inhibitor, a polymer type scale preventing dispersant and a bactericidal algaecide, and is used for preventing impurities in phosphoric acid from forming scale in production equipment and pipelines in the phosphoric acid manufacture by a wet method. At present, inventions or products similar to the agent are not discovered. The scale preventing agent of the present invention is used in the phosphoric acid manufacture by a wet method, and the scale eliminating period is extended to 30 to 100 days from the original 3 to 5 days.

Description

Scale inhibitor for wet method phosphoric acid manufacture
Technical field
The present invention relates to chemical fertilizer manufacturing technology field, especially a kind ofly in Wet-process Phosphoric Acid Production, be used for stoping the composition of phosphoric acid impurity in equipment and pipeline fouling.
Background technology
Manufacture method by phosphoric acid by wet process is determined, contains a large amount of impurity in the phosphoric acid by wet process, as Ca 2+, Mg 2+, Fe 3+, Na +, K +, Pb +, Zn 2+Deng metal ion, also has SO 4 2-Silicate, the precipitable crystallinity salt that sial acid group and they have constituted, in addition, the organism that also has gel-like, because this a large amount of one-tenth dirt material exists, make the production unit and the pipeline of phosphoric acid by wet process produce serious fouling and cause the shutoff phenomenon, generally at least three or five days, five or six days just because of the obstruction cleaning of being forced to stop production at most, not only cause very big trouble burden and loss and waste, and have a strong impact on equipment effectiveness and productivity because of breaks in production, stop the fouling of phosphoric acid by wet process, never be well solved as the great problem of present domestic phosphorus ammonium industry at equipment and pipeline.The method that is adopted is a heating method, alleviate the formation of fouling by heated phosphoric, but this method can cause serious corrosion damage to equipment and pipeline, is not long-term plan.
Summary of the invention
The invention provides a kind of scale inhibitor for wet method phosphoric acid manufacture, the problem that it mainly solves is to hinder and delay the fouling of phosphoric acid on production unit and pipeline.
For solving the fouling of phosphoric acid on production unit and pipeline, Scale inhibitors of the present invention is a kind of by organic phosphine class anti-incrustation corrosion inhibitor and polymer class dirt dispersion agent, and the Biocidal algae-killing agent compounded combination forms.
The weight ratio of above-mentioned each constituent can be: described organic phosphine class anti-incrustation corrosion inhibitor is 20%～50%, and described polymer class dirt dispersion agent is 20%～40%, and described Biocidal algae-killing agent is 10%～40%.
Above-mentioned organic phosphine class anti-incrustation corrosion inhibitor can be following material one or more combinations:
A. Amino Trimethylene Phosphonic Acid (ATMP);
B. 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP);
C. diethylene triamine pentamethylene phosphonic (DTPMP);
D. ethylene diamine tetra methylene phosphonic acid (EDTMP);
E. hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA);
F. the phosphonic acids butane 1,2,4 tricarboxylic acid (PBTCA).
These organic phosphine class anti-incrustation corrosion inhibitor Stability Analysis of Structures be difficult for to be decomposed, and are nontoxic or low toxicity is pollution-free, form inner complex, complex compound with metal ion, and have good scale inhibition effect and have tangible molten limit effect.During with other dirt dispersion agents, the compound use of Biocidal algae-killing agent, have obvious synergistic, can good scale effect all be arranged,, can reach good scale inhibitor effect with the composite use of dispersion agent to calcium sulfate, lime carbonate and calcium phosphate.
One or more combinations that above-mentioned polymer class dirt dispersion agent can be following material:
A. polyacrylic acid (PAA);
B. sodium polyacrylate (PAAS);
C. hydrolysis maleic anhydride;
D. toxilic acid acrylic copolymer (MA-AA);
E.AA-MA-AMPS Hypophosporous Acid, 50 tetrapolymer;
F. vinylformic acid-Propylene glycol monoacrylate multipolymer;
G. vinylformic acid-2 acrylamide-2 methyl propane sulfonic acid multipolymer;
H, allyl sulphonic acid salt copolymer.
Above-mentioned these polymer class dirt dispersion agents have the monomer autopolymer, and more some more is multipolymers, and they can both be scattered in salt crystallites such as lime carbonate, calcium sulfate and calcium phosphate or silt and not precipitate in the liquid phase, thereby reach the purpose of scale inhibition.Can with organic phosphonate, the compound use of zinc salt, the multipolymer that has to calcium sulfate, lime carbonate particularly calcium phosphate scale formation and deposit good inhibition effect, to ferric oxide, mud, clay and grease also have good dispersing property.Terpolymer (AA/AMPS) has bigger calcium tolerance to the calcium phosphate in the system, lime carbonate, calcium sulfate and zinc calcium, dispersity and good scale effect owing to contain the carboxylic acid group and the strong polar sulfonic group of scale inhibition and dispersion performance in the molecular structure.
Above-mentioned Biocidal algae-killing agent can be dodecyl benzyl dimethyl ammonium chloride (1227).
Therefore the compound of forming by organic phospho acid, poly carboxylic acid, co-polymer of sulfonate, have chelating, dispersing property, it can make crystal generation lattice distortion, thereby makes intergranule be difficult to form densification and firm dirt layer, and its dispersing property makes particulate be difficult to contact-impact again and coalescent.Particulate can be dispersed in the long period can not become dirt in the liquid phase, a large amount of dense electric charges on the polymer molecule, cause calcium ion to be attracted in a large number around the macromole, therefore these calcium ions have reduced the possibility that is combined into dirt with inorganic anion and have reduced sedimental generation, thereby play scale effect, the sodium polyacrylate of 1PPM concentration can tack 45 times calcium ion by sequestering action.Vinylformic acid and the multipolymer of acrylamide can not only stop lime carbonate, calcium phosphate to become dirt, can also dispersing iron oxide, earth, mud etc., can be in the high rigidity system deposition of inhibited oxidation iron and molysite.
Multiple copolymer to the scale inhibition performance of calcium phosphate obviously greater than the elemental body polymkeric substance, for example:
Title Scale inhibition performance to calcium phosphate
Sodium polyacrylate 34％
Vinylformic acid and Propylene glycol monoacrylate multipolymer 72％
Terpolymer (vinylformic acid, Propylene glycol monoacrylate, many propylidene of vinylformic acid hydroxyl oxygen ester) 82％
When consumption reached every gram phosphoric acid and adds 10 micrograms, they were as follows to ferric oxide and argillous dispersive ability:
Title To the ferric oxide dispersive ability To the earth dispersive ability
Sodium polyacrylate 45％ 68％
Vinylformic acid and Propylene glycol monoacrylate multipolymer 83.6％ 84.6％
Owing to adopted such scheme, the present invention to have tangible scale inhibition effect:
Actual production with phosphoric acid by wet process is an example, and when not adding Scale inhibitors of the present invention, its production unit and pipeline just stopped up the cleaning of being forced to stop production because of fouling in 3～5 days in production at most; And after adding Scale inhibitors of the present invention, after its production unit and pipeline generation fouling obstruction need the time of stopping production cleaning then to can be extended down to 30～100 days.
Embodiment:
Product of the present invention is in the compounded combination of multiple series, by test its scale inhibition performance, through screening, get in excellent excellently, adopt following compounded combination prescription according to qualifications according to price-efficiency ratio:
Embodiment 1: making the double centner scale inhibitor for wet method phosphoric acid manufacture, is that each raw material with following formula ratio mixes:
Amino Trimethylene Phosphonic Acid (ATMP) 12 kilograms
Diethylenetriamine five methene phosphoric acid (DTPMP) 12 kilograms
Vinylformic acid-2 acrylamide-2 methyl propane sulfonic acid terpolymer (AA/AMPS) 50 kilograms
The allyl sulphonic acid salt copolymer 20 kilograms
Dodecyl benzyl dimethyl ammonium chloride (1227) 6 kilograms
Embodiment 2: making the double centner scale inhibitor for wet method phosphoric acid manufacture, is that each raw material with following formula ratio mixes
Polyacrylic acid (PAA) 40 kilograms
1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 25 kilograms
2-hydroxyl phosphate acetate (HPAA) 25 kilograms
Dodecyl benzyl dimethyl ammonium chloride (1227) 10 kilograms
Embodiment 3: making the double centner scale inhibitor for wet method phosphoric acid manufacture, is that each raw material with following formula ratio mixes:
Amino Trimethylene Phosphonic Acid 20 kilograms
Toxilic acid and acrylic copolymer (MA/AA) 25 kilograms
Vinylformic acid-Propylene glycol monoacrylate multipolymer (AA/HPA) 25 kilograms
Polyacrylic acid (PAA) 25 kilograms
Dodecyl benzyl dimethyl ammonium chloride (1227) 5 kilograms
Embodiment 4: making the double centner scale inhibitor for wet method phosphoric acid manufacture, is that each raw material with following formula ratio mixes:
Amino Trimethylene Phosphonic Acid (ATMP) 10 kilograms
Diethylenetriamine five methene phosphoric acid (DTPMP) 15 kilograms
Vinylformic acid-2 acrylamide-2 methyl propane sulfonic acid terpolymer (AA/AMPS) 15 kilograms
Vinylformic acid-Propylene glycol monoacrylate multipolymer (AA/HPA) 10 kilograms
Polyacrylic acid (PAA) 30 kilograms
Maleic anhydride and acrylic copolymer (CPMA) 10 kilograms
Dodecyl benzyl dimethyl ammonium chloride (1227) 5 kilograms
The allyl sulphonic acid salt copolymer 5 kilograms
The scale inhibitor for wet method phosphoric acid manufacture that adopts above four Example formulations to make is applicable to the purification of the phosphoric acid by wet process that uses Yunnan, Guizhou, Hubei, the different qualities of the different mineral resources gained in Sichuan.Filter the back with 10～100PPM consumption at phosphoric acid and add or add, can keep in 30～100 days and exempt big fill from dilute phosphoric acid sedimentation storage tank exit.If consumption adds to the chemical pickling agent that 200～400PPM can be used as the phosphoric acid dirt.

Claims (2)

1. scale inhibitor for wet method phosphoric acid manufacture, it is characterized in that: it is combined by organic phosphine class anti-incrustation corrosion inhibitor, polymer class dirt dispersion agent and Biocidal algae-killing agent, the weight ratio of its constituent is: described organic phosphine class anti-incrustation corrosion inhibitor is 20%～50%, described polymer class dirt dispersion agent is 20%～40%, and described Biocidal algae-killing agent is 10%～40%.
2. scale inhibitor for wet method phosphoric acid manufacture according to claim 1 is characterized in that: described organic phosphine class anti-incrustation corrosion inhibitor is one or more combinations of following material:
A. Amino Trimethylene Phosphonic Acid;
B. 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid;
C. diethylene triamine pentamethylene phosphonic;
D. ethylene diamine tetra methylene phosphonic acid;
E. hydroxyethylidene diphosphonic acid guanidine-acetic acid;
F. the phosphonic acids butane 1,2,4 tricarboxylic acid;
One or more combinations that described polymer class dirt dispersion agent is following material:
A. polyacrylic acid;
B. sodium polyacrylate;
C. hydrolysis maleic anhydride;
D. toxilic acid acrylic copolymer;
E.AA-MA-AMPS Hypophosporous Acid, 50 tetrapolymer;
F. vinylformic acid-Propylene glycol monoacrylate multipolymer;
G. vinylformic acid-2 acrylamide-2 methyl propane sulfonic acid multipolymer;
H, allyl sulphonic acid salt copolymer;
Described Biocidal algae-killing agent is a dodecyl benzyl dimethyl ammonium chloride.
CNB2005102005053A 2005-08-31 2005-08-31 Scale inhibitor for wet method phosphoric acid manufacture Expired - Fee Related CN100431985C (en)

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WO2023199013A1 (en) * 2022-04-11 2023-10-19 Independence Oilfield Chemicals Llc Compositions comprising polymer, scale inhibitor and quaternary ammonium compound, method and uses.

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US8980101B2 (en) * 2008-09-04 2015-03-17 Nalco Company Method for inhibiting scale formation and deposition in membrane systems via the use of an AA-AMPS copolymer
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CN1458172A (en) * 2003-04-20 2003-11-26 高同柱 Polynary copolymer containing ether phosphonic acid and sulfon carboxylic acid and process for preparing multifunctional water treating agent

Cited By (2)

* Cited by examiner, † Cited by third party
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CN101798146A (en) * 2010-03-24 2010-08-11 王显平 Solid composite sterilizing scale inhibiting agent
WO2023199013A1 (en) * 2022-04-11 2023-10-19 Independence Oilfield Chemicals Llc Compositions comprising polymer, scale inhibitor and quaternary ammonium compound, method and uses.

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