CN100573027C - The Phosphoric Acid Concentration descaling method of heat exchanger of graphite - Google Patents
The Phosphoric Acid Concentration descaling method of heat exchanger of graphite Download PDFInfo
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- CN100573027C CN100573027C CNB2005100031320A CN200510003132A CN100573027C CN 100573027 C CN100573027 C CN 100573027C CN B2005100031320 A CNB2005100031320 A CN B2005100031320A CN 200510003132 A CN200510003132 A CN 200510003132A CN 100573027 C CN100573027 C CN 100573027C
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- Prior art keywords
- heat exchanger
- cleaning
- cleaning fluid
- graphite
- phosphoric acid
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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
-
- 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
Abstract
The invention discloses a kind of descaling method of Phosphoric Acid Concentration heat exchanger, this method is to adopt a kind of cleaning fluid of being made up of rare silicate fluoride solution, organic phosphonic acid anticorrosion agent and film forming matter, and cleans the technology of removing fouling with cleaning fluid again behind the first water cleaning heat exchanger.In the cleaning fluid, fluosilicic acid is 5%～20% diluted acid; Organic phosphonic acid anticorrosion agent is ATMP, hydroxy ethylene diphosphonic acid and hydroxyl 1, the 1-ethylidene diphosphonic acid; Film forming matter is nitrosophenyl hydroxylamine amine ammonium salt and methenamine and sodium molybdate.Add the surfactant alkylsulfonate during use.The descalling technique of Phosphoric Acid Concentration heat exchanger of the present invention, can remove the fouling of graphite heat exchanger efficiently, up hill and dale, controlled simultaneously the corrosion of cleaning fluid effectively to equipment, compare with traditional cleaning method, this method cleaning frequency prolongs, scavenging period shortens at every turn, clean thoroughly, the graphite heat exchanger heat transfer efficiency increases substantially, thereby has improved the production capacity of equipment.
Description
Technical field
The present invention relates to remove the method for fouling, also relate to the preparation of cleaning fluid and sustained release agent thereof, in particular to the descaling method of Phosphoric Acid Concentration heat exchanger at material surface.
Background technology
Phosphoric acid,diluted in the wet method phosphoric acid manufacture process process concentrates the overwhelming majority and adopts graphite heat exchanger, in the concentrated phosphoric acid process, there is a large amount of dirts to generate on the heat exchange equipment inwall, the graphite-pipe inwall of the impregnated phenolic resin constantly dirt layer of thickening has a strong impact on graphite heat exchanger heat exchange effect, causes phosphoric acid,diluted to concentrate production capacity and descends significantly.Traditional descaling method adopts giant cleaning and dilute sulfuric acid to clean and combines, facts have proved that this method can not be with the thoroughly removing of dirt layer, cause dirt constantly to be piled up, cause concentrated actual motion ability to reduce gradually, can cause the mechanical damage of dipping graphite tube simultaneously.For scale removal, the cleaning frequency is forced to shorten gradually.In recent years, people have studied some and have removed the method and the cleaning agent of fouling, as No. 88105662 " a kind of chemical cleaning solution of heavy grease ", No. 91105354.9 " compound methods of aluminum heat exchanger pickling sustained release agent " of Chinese patent application, No. 02812333.6 " improved dirt conditioner " etc.But by retrieval, do not see as yet and can efficiently wash the bibliographical information of Phosphoric Acid Concentration heat exchanger fouling clearly.
Summary of the invention
Purpose of the present invention just is to provide the technology of the employed heat exchanger of graphite fouling of a kind of efficient cleaning Phosphoric Acid Concentration, to overcome the shortcoming of conventional clean descalling technique.
Solution of the present invention is at the chemical composition of Phosphoric Acid Concentration heat exchanger fouling and crystalline phase characteristics thereof, adopt a kind of cleaning fluid of the especial manufacture of forming by rare silicate fluoride solution, organic phosphonic acid anticorrosion agent and film forming matter, and clean the technology of removing fouling with cleaning fluid again behind the first water cleaning heat exchanger.
The three-component system that special cleaning fluid provided by the invention is made up of rare silicate fluoride solution, organic phosphonic acid anticorrosion agent and film forming matter, wherein:
The mass fraction of fluosilicic acid is 5%～20%;
Organic phosphonic acid anticorrosion agent has ATMP (ATMP), HEDP (hydroxy ethylene diphosphonic acid) and HEDPA (hydroxyl 1,1-ethylidene diphosphonic acid), and use amount is 10～200mg/L;
Film forming matter has cupferron (nitrosophenyl hydroxylamine amine ammonium salt), methenamine and sodium molybdate etc., and use amount is in 10～200mg/L scope, as film forming matter.
In above-mentioned cleaning fluid, fluosilicic acid has good scale removal activity, and through test, 20% fluosilicic acid reaches 100% to the dissolution rate of graphite heat exchanger fouling; The corrosion that the graphite-pipe that draws impregnated phenolic resin of molten dirt test can bear fluosilicic acid, fluosilicic acid is again the accessory substance of phosphoric acid by wet process, uses economy, convenient, therefore first-selected fluosilicic acid is made the main component of graphite-pipe cleaning solution for descaling.
Though fluosilicic acid has descale effect preferably, can not ignore the corrosion of Phosphoric Acid Concentration system internal circulation pump equipment and materials, therefore must add sustained release agent.The inventor reaches corrosion inhibiter more than 95% as target the corrosion inhibition rate of 904L stainless steel material in 60 ℃ corrosive medium, promptly in the fluosilicic acid that adds corrosion inhibiter, the stainless corrosion rate of 904L and they (normal running temperature when phosphoric acid,diluted concentrates) corrosion rate in SPA (circulation composition when phosphoric acid,diluted is concentrating) under 75～88 ℃ of temperature is suitable, make it can be a comparatively safe scope, and take into account the CD4MCu stainless steel material corrosion mitigating effect is preferably also arranged, take into full account environmental protection, economical, reliable and principle easily, through repetition test, filter out organic phosphonic acid anticorrosion agent as one of formula components of this cleaning agent.
Filmogen is the inhibition auxiliary agent, and they form film on the metal surface, stops the etch of fluosilicic acid to metal.
In cleaning process, should add surfactant, it is a kind of alkylsulfonate of 12～16 carbon atoms, its use amount is at 10～50mg/L, this is because surfactant can make the surface tension of water or cleaning fluid reduce, thereby the tube wall of wetting graphite-pipe, water or cleaning fluid can disperse between tube wall and dirt layer very soon, can quicken the dissolving of dirt layer.
The process of cleaning of the present invention is: when graphite heat exchanger is cleaned, adopted giant cleaning heat exchanger earlier about 12 hours, then, effluent sewerage; Start and clean liquid pump, ready cleaning fluid and the surfactant of being furnished with corrosion inhibiter all got to the concentration and evaporation chamber, with steam cleaning fluid is heated to 60 ℃, keep this temperature operation after 12 hours by cleaning the driving program, discharge and clean the soiling solution that produces, finish to clean.About 40 hours of cleaning and cleaning required time.Used cleaning fluid after each group component of cleaning fluid is filled in supplement as required, reuses by analysis.
The descalling technique of Phosphoric Acid Concentration heat exchanger of the present invention, can remove the fouling of graphite heat exchanger efficiently, up hill and dale, clean back heat exchanger graphite-pipe inwall and do not have any attachment, controlled simultaneously the corrosion of cleaning fluid effectively to equipment, stainless steel smooth surfaces such as concentration axial flow pump flow passage components, metal luster, no evidence of corrosion.Compare with traditional sulfuric acid cleaned method, the cleaning frequency of this method cleaned from average per 15 days and once extends to per 20 days once, and each time of cleaning foreshortened to 12 hours greatly from 20 hours, and therefore, increased to 300 day from 285 days a running time in year that concentrates production.Because more thorough to the cleaning of fouling, the graphite heat exchanger heat transfer efficiency increases substantially, thereby has improved the production capacity of equipment, and to the competitiveness of the technical merit, economic benefit and the industry that promote to improve phosphatic fertilizer company, positive effect will be arranged.
The specific embodiment
Embodiment is an example with the Phosphoric Acid Concentration graphite heat exchanger cleaning and descaling technology of Guangzhou Hongfu Industrial Development Co., Ltd.The said firm's Phosphoric Acid Concentration adopts typical vacuum forced circulation concentration flow path, and its capital equipment has graphite heat exchanger, vaporization chamber and circulating pump etc., and the phosphoric acid production scale is for producing 500000 tons per year.In the fouling of graphite heat exchanger mainly by CaSO
4And the MgSO of trace
4And SiO
2Form.At this fouling, filter out a kind of new cleaning fluid, successfully solved a graphite heat exchanger fouling cleaning technique difficult problem, and 904L and CD4MCu stainless steel corrosion inhibition rate reach more than 95%.The three component system that the cleaning fluid of development is made up of rare silicate fluoride solution, organophosphor agent and film forming matter, wherein:
The fluosilicic acid mass fraction is 5%～20%;
The organic phosphates corrosion inhibiter has ATMP (ATMP), HEDP (hydroxy ethylene diphosphonic acid) and HEDPA (hydroxyl 1,1-ethylidene diphosphonic acid), and use amount is 10～200mg/L;
Film forming matter has cupferron (nitrosophenyl hydroxylamine amine ammonium salt) and methenamine and sodium molybdate, and use amount is in 10～200mg/L scope;
Surfactant is that a kind of carbon number is 12～16 alkylsulfonate, and use amount is 10～50mg/L.
When graphite heat exchanger is cleaned, adopted giant cleaning heat exchanger earlier about 12 hours, then, effluent sewerage; Start and clean liquid pump, ready cleaning fluid and the surfactant of being furnished with corrosion inhibiter all got to the concentration and evaporation chamber, with steam cleaning fluid is heated to 60 ℃, keep this temperature operation after 12 hours by cleaning the driving program, discharge and clean the soiling solution that produces, finish to clean.About 40 hours of cleaning and cleaning required time.
Cleaning performance such as following table:
Claims (4)
1 one kinds of Phosphoric Acid Concentration descaling method of heat exchanger of graphite, it is characterized in that this method is to adopt a kind of cleaning fluid of being made up of rare silicate fluoride solution, organic phosphonic acid anticorrosion agent and film forming matter, and clean the technology of removing fouling with cleaning fluid again behind the first water cleaning heat exchanger; In the described cleaning fluid, the mass fraction of fluosilicic acid is 5%～20%;
Organic phosphonic acid anticorrosion agent has ATMP, hydroxy ethylene diphosphonic acid and hydroxyl 1, the 1-ethylidene diphosphonic acid, and use amount is 10～200mg/L;
Film forming matter has nitrosophenyl hydroxylamine amine ammonium salt and methenamine and sodium molybdate, and use amount is 10～200mg/L.
2 according to the descaling methods of the described Phosphoric Acid Concentration of claim 1 with heat exchanger of graphite, it is characterized in that adding a kind of carbon number and be 12～16 alkyl sulfonate surfactants in cleaning process, and its use amount is 10～50mg/L.
3 according to the descaling method of the described Phosphoric Acid Concentration of claim 1 with heat exchanger of graphite, it is characterized in that the technological process of scale removal is: adopted giant cleaning heat exchanger earlier about 12 hours, then, effluent sewerage; Start and clean liquid pump, ready surfactant and the cleaning fluid of being furnished with organic phosphonic acid anticorrosion agent are all got to the concentration and evaporation chamber, with steam cleaning fluid is heated to 60 ℃, keep this temperature operation after 12 hours by cleaning the driving program, discharge and clean the soiling solution that produces, finish to clean.
4 according to the descaling methods of the described Phosphoric Acid Concentration of claim 1 with heat exchanger of graphite, used cleaning fluid by analysis after, after each group component of cleaning fluid is filled in supplement as required, recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100031320A CN100573027C (en) | 2005-07-15 | 2005-07-15 | The Phosphoric Acid Concentration descaling method of heat exchanger of graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100031320A CN100573027C (en) | 2005-07-15 | 2005-07-15 | The Phosphoric Acid Concentration descaling method of heat exchanger of graphite |
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| Publication Number | Publication Date |
|---|---|
| CN1724965A CN1724965A (en) | 2006-01-25 |
| CN100573027C true CN100573027C (en) | 2009-12-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108019188A (en) * | 2017-10-31 | 2018-05-11 | 中盐皓龙盐化有限责任公司 | A kind of pickling descaling method suitable for Salt mine underground shaft protective casing km waterflood-transmission line |
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| CN100463958C (en) * | 2006-06-05 | 2009-02-25 | 太仓市宝马环境工程有限公司 | Degreased cleaning agent |
| CN101105118B (en) * | 2006-07-11 | 2010-06-30 | 成都孚吉科技有限责任公司 | Solid anti-scaling agent and preparation process thereof |
| CN101555441B (en) * | 2008-04-09 | 2012-03-21 | 中国神华能源股份有限公司 | Cleaning agent and cleaning process of GGH heat exchange component |
| CN101530675B (en) * | 2009-04-21 | 2011-11-09 | 瓮福（集团）有限责任公司 | Method for delaying deposition of sieve plate of extraction column |
| 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 |
| CN101786613B (en) * | 2009-11-18 | 2012-07-04 | 瓮福（集团）有限责任公司 | Method for inhibiting scales of wet-process phosphoric acid concentration heat exchanger |
| CN101774558B (en) * | 2009-12-25 | 2011-10-19 | 中国海洋石油总公司 | Method for improving yield of concentrated phosphoric acid |
| US8900539B2 (en) | 2011-03-22 | 2014-12-02 | Cytec Technology Corp. | Preventing or reducing scale in wet-process phosphoric acid production |
| CN102205947A (en) * | 2011-04-12 | 2011-10-05 | 瓮福（集团）有限责任公司 | Method for cleaning heat exchanger used in extraction of iodine from phosphoric acid by using wet process |
| CN102506608A (en) * | 2011-10-08 | 2012-06-20 | 瓮福（集团）有限责任公司 | Method for cleaning wet-method phosphoric acid concentration heat exchanger |
| CN102519301A (en) * | 2011-12-09 | 2012-06-27 | 贵州开磷（集团）有限责任公司 | Method for washing scales formed on tube of graphite heat exchanger |
| CN102538572B (en) * | 2012-02-03 | 2013-10-23 | 湖北双环科技股份有限公司 | Method for cleaning spiral-plate heat exchanger |
| CN102746954A (en) * | 2012-07-23 | 2012-10-24 | 瓮福（集团）有限责任公司 | Cleaning agent for cleaning filter cloth for producing crystalline monoammonium phosphate by raffinate |
| CN103121023A (en) * | 2013-01-28 | 2013-05-29 | 江苏国正新材料科技有限公司 | Washing method for electrical carbon material |
| BR122020006607B1 (en) | 2014-02-11 | 2022-08-09 | Cytec Industries Inc | PROCESS OF INHIBITION OF INCRUSTATION PRODUCED DURING THE PRODUCTION OF WET PROCESS PHOSPHORIC ACID |
| CN104588381A (en) * | 2014-12-30 | 2015-05-06 | 铜陵鑫克精细化工有限责任公司 | Cleaning method for extraction plant capable of purifying wet process phosphoric acid with solvent extraction method |
| CN107635917B (en) | 2015-02-11 | 2021-04-30 | 塞特工业公司 | Modified amines useful as scale inhibitors in wet-process phosphoric acid production |
| CN106520419A (en) * | 2016-08-31 | 2017-03-22 | 瓮福达州化工有限责任公司 | Cleaning solution of wet phosphoric acid purification, pretreatment and concentration system |
| CN109896640B (en) * | 2019-03-21 | 2022-11-29 | 云南磷化集团有限公司 | Efficient wet-process phosphoric acid graphite heat exchanger scale inhibitor, preparation method and application |
| RU2019126815A (en) * | 2019-08-26 | 2021-02-26 | Ангара Индастриз Лтд. | Cognitive purification systems and methods |
-
2005
- 2005-07-15 CN CNB2005100031320A patent/CN100573027C/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108019188A (en) * | 2017-10-31 | 2018-05-11 | 中盐皓龙盐化有限责任公司 | A kind of pickling descaling method suitable for Salt mine underground shaft protective casing km waterflood-transmission line |
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| CN1724965A (en) | 2006-01-25 |
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