WO2017011010A1 - Procédé de formation d'une composition de détartrage - Google Patents

Procédé de formation d'une composition de détartrage Download PDF

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Publication number
WO2017011010A1
WO2017011010A1 PCT/US2015/040628 US2015040628W WO2017011010A1 WO 2017011010 A1 WO2017011010 A1 WO 2017011010A1 US 2015040628 W US2015040628 W US 2015040628W WO 2017011010 A1 WO2017011010 A1 WO 2017011010A1
Authority
WO
WIPO (PCT)
Prior art keywords
bone meal
composition
dimethylamine
descaling
macerated
Prior art date
Application number
PCT/US2015/040628
Other languages
English (en)
Inventor
Ilan FRIEDMAN
Original Assignee
Friedman Ilan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Friedman Ilan filed Critical Friedman Ilan
Priority to PCT/US2015/040628 priority Critical patent/WO2017011010A1/fr
Priority to US15/741,904 priority patent/US10487298B2/en
Publication of WO2017011010A1 publication Critical patent/WO2017011010A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/06—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/40—Products in which the composition is not well defined
    • C11D7/46—Animal products
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention relates to descaling compositions. More particular, the present invention relates to a process for forming such descaling compositions. Additionally, the present invention relates to descaling compositions that can be used for the removal of scale from process equipment used in the energy industry. The present invention also relates to processes for the descaling of processing towers.
  • Scaling is the accumulation of unwanted material on solid surfaces to the detriment of the function.
  • the scaling material can consist of either living organisms are non-living substances, organic or inorganic. Scaling is a common and diverse phenomenon. Scaling can occur on the ship hulls, scaling of heat transfer components throughout process industries, and deposits found on a variety of other structures.
  • Scaling can also incur on injection/spray nozzles. As a result, this can cause an incorrect amount of injected fluid, a malformed jet, component inefficiency and component failure. Whenever scaling occurs in the production zone of petroleum reservoirs and oil wells, this can result in decreased petroleum production, plugging, and an actual stoppage of flow. Whenever these issues occur, in order to properly descale the particular item, a shutdown of the facilities is often required. The shutdown can reduce production time and increase costs.
  • biosides can be applied so as to reduce scaling.
  • biosides can include inorganic chlorine and bromide compounds, chlorine and bromide cleavers, ozone oxygen cleavers, and unoxidizable biosides.
  • unoxidizable biosides is a mixture of chloromethyl-isothiazolinone and methyl-isothiazolinone.
  • Chemical scaling inhibitors can reduce scaling in many systems by interfering with the crystallization, attachment or consolidation steps of the scaling process. These can include chelating agents, long-chain aliphatic ammines or polyamines, organic phosphonic acids, polyelectrolytes, and polymethacrylic acid. In the case of boilers, aluminum or magnesium additives can serve to avoid such scaling.
  • each of these components can often be toxic to the environment and can require the persons applying the descaling agents to wear specialized equipment to prevent exposure to such toxic chemicals.
  • Chemical or mechanical cleaning processes for the removal of deposits and scales are used when the scaling reaches the point of impacting the performance of the system. These processes comprise pickling with acids and complexing agents, cleaning with pipe-velocity water jets, recirculating or blasting with metal, or propelling off-line mechanical bullet-type tube cleaners.
  • the chemical cleaning causes environmental problems through handling, application, storage and disposal of chemicals.
  • the mechanical cleaning can be an environmentally friendlier solution though often requires a great deal of time, equipment and costs. As such, a need has developed so as to provide a descaling solution that can be applied which is non-toxic, extremely effective, and reduces facility downtime.
  • This composition includes an aqueous solution containing from 5 to 25% of hydrogen chloride, and between 0.1 and 1 % of an organic nitrogen base soluble in the hydrochloric acid.
  • the organic nitrogen base can be either an aromatic or heterocyclic nitrogen base.
  • the composition also includes from 0.1 to 2% of the water-soluble thiocyanate.
  • U.S. Patent No. 3,025,225 issued on March 13, 1962 to Snyder et al, discloses an electrolytic acid for the descaling of metals.
  • This descaling composition is in a bath that include 60% to 95% of sulfuric acid, 0.5% to 20% of hydrofluoric acid, 0.001% of sulfite ions, 0 to 0.5% of orthophosphoric acid, and the remainder being water.
  • U.S. Patent No. 3,030,239 issued on April 17, 1962 to Mekjeam et al., teaches a process for the descaling of metals.
  • the metal to be treated receives between 50 to 90% of an alkali metal hydroxide, 2 to 25% of an alkali metal phosphate, 0.5% to 30% of an alkali metal carbonate, and 0.5 to 25% of a material selected from the group of alkali metal halide, alkaline earth metal halides, and mixtures thereof.
  • U.S. Patent No. 3,121,026, issued on February 11, 1964 to Beigay discloses the descaling of metals and alloys with aqueous potassium hydroxide. The process is intended to remove metal oxide scale on a surface thereof. The article is brought into contact with an aqueous bath that contains 60 to 90% potassium chloride oxide and at least 10% water while maintaining the bath at a temperature between 300° F to 450° F.
  • U.S. Patent No. 3,277,008, issued on October 4, 1966 to A. H. Heit discloses a surface cleaning method and composition.
  • this composition serves to descale internal metal surfaces of a jacket of glass-lined jacketed equipment while preventing spallation of the glass lining.
  • An aqueous acid solution contains between 2 and 20% of an alpha-beta ethylenically unsaturated, water-soluble carboxylic acid.
  • the carboxylic gas serves to react with insoluble phosphates, carbonates, and hydroxide to produce water-soluble compounds.
  • U.S. Patent No. 4,439,339 provides a descaler composition and method for the removal of scale from freshwater production equipment such as desalinators or evaporators, along with distillation units, heat exchangers and boilers.
  • the composition includes a blend of acids of various strengths so as to provide a timed release effect.
  • the acids include hydrochloric acid, dichloroacetic acid, and acetic acid.
  • the composition further contains a surfactant, such as isopropyl alcohol, which reacts with the acids.
  • the composition further includes an acid-based indicator to signify neutralization of the acidizer during scale removal.
  • U.S. Patent No. 5,575,857 issued on November 19, 1996 to Lunski et al, provides an aqueous alkaline metal descaling concentrate. This process includes the steps of applying an aqueous solution containing alkali metal carbonate salts and a hydro trope so as to remove organic scale. Additionally, the composition further includes a mixture of potassium and sodium carbonate salts.
  • It is further object of the present invention provide a process for the forming of a descaling composition in which the descaling composition will not degrade the material upon which it is applied.
  • It is another object of the present invention provide a process for the forming of a descaling composition in which the descaling composition can extend the life of the equipment to which it is applied.
  • It is another object of the present invention provide a process for the formation of a descaling composition in which the descaling composition is operator- friendly.
  • the present invention is a process for forming a descaling composition that includes the steps of : ( 1 ) macerating a bone meal with a dimethylamine solution; (2) digesting the macerated bone meal with hydrochloric acid; (3) neutralizing the digested bone meal with calcium oxide; (4) treating the neutralized bone meal with sulfuric acid; and (5) applying a refiuxing treatment with dimethylamine and hydrazine hydrate.
  • the step of macerating includes adding the bone meal to the dimethylamine solution.
  • the dimethylamine solution has a 10% concentration.
  • the step of macerating is carried out over a period of eight hours.
  • the macerated bone meal solids are removed from the dimethylamine solution and then transferred to an extraction tower prior to the step of digesting.
  • the step of a digesting include circulating the hydrochloric acid through the macerated bone meal. The circulating is for a period of time of eight hours at room temperature.
  • the step of digesting further includes decreasing the temperature of the digested bone meal for another period of time. The temperature is decreased to approximately 16°C for a period of time of approximately two hours.
  • the step of digesting further includes allowing the mixture of the hydrochloric acid and the macerated bone meal to rise to ambient temperature following the step of decreasing the temperature. Solids are removed from the digested bone meal and the hydrochloric acid.
  • the step of neutralizing includes washing the calcium oxide and the digested bone meal with water such that the calcium oxide in the digested bone meal has a pH of approximately 7.
  • the neutralized bone meal is then dried.
  • the neutralized bone meal is dried so as to have a humidity of less than 20% water.
  • the step of treating includes a step of adding the dried bone meal to the sulfuric acid in a reactor and then agitating the sulfuric acid and the dried bone meal in the reactor. Following agitation, the sulfuric acid and the dried bone meal are allowed to stand for a period of time. This period of time is approximately three hours. The sulfuric acid will have a concentration of 98%.
  • the treated bone meal and the sulfuric acid are filtered so as to produce a liquid phase and a solid phase prior to the step of applying a refluxing treatment.
  • the liquid phase contains phosphated amine.
  • the mixture is refluxed treated for a period of time. This period of time is approximately eight hours.
  • the dimethylamine is of a 3% concentration.
  • the mixture is cooled.
  • the process of the present invention produces a phosphated descaler for process equipment and includes an antioxidant complex to prevent metal oxidization.
  • the process of the present invention utilizes bone meal.
  • the bone meal is macerated with dimethylamine.
  • the mixture is digested with hydrochloric acid.
  • hydrochloric acid Following digestion, it is neutralized with calcium oxide.
  • the resulting solids are treated with sulfuric acid.
  • a refluxing treatment is then carried out with dimethylamine and hydrazine hydrate.
  • the dimethylamine solution is prepared to a 10% concentration.
  • the bone meal is left to macerate in the dimethylamine solution for a period of eight hours at 40°C.
  • the bone meal is removed by decanting and the dimethylamine solution continues to macerate for second, third and fourth batches.
  • the solution is discarded after treating in the fourth batch.
  • the solids macerated in the dimethylamine are transferred to an extraction tower for meal digestion. Concentrated hydrochloric acid is circulated therethrough and then recirculated for eight hours at room temperature. After eight hours, the temperature is decreased to 16°C. The hydrochloric acid continues to recirculate for an additional two hours. The mixture is left so as to return to ambient temperature. The solids are then removed from the digester and calcium oxide is introduced therewith. The solids in the calcium oxide are washed with water so as to achieve a pH of 7. If necessary, additional calcium oxide can be added. The solids are then heated on a stove and dried to a humidity of less than 20% water.
  • Sulfuric acid is added in a glazed reactor.
  • the sulfuric acid is 98% sulfuric acid.
  • the solids are slowly added with agitation. Once all of the solids have been added, the agitator is turned off and the mixture is allowed to stand for more than three hours.
  • the slurry is then filtered.
  • the liquid phase will contain the phosphate amine. 3% dimethylamine and hydrazine hydrate are then added. These are mixed in heated under reflux treatment for a period of eight hours. Subsequently, the mixture is cooled and available for packing and packaging.
  • the composition that results from this process is a descaler for process equipment, such as heat exchangers, distillation towers, turbines, offshore installations, processing towers, docking facilities, gas line flow stations and pipelines, gas separators, radiators, coils, evaporators, condensers, gas sweetening plants, and a variety of other process equipment.
  • the composition can be used for cleaning, metal oxidation removal, and removal of encrusted salts, such as silica, ammines and carbonates.
  • the composition is excellent for stainless steel passivation.
  • the composition can also remove those encrustations that are generated in the processing of oil and gas.
  • the composition of the present invention is reusable. As such, it can be used several times, depending upon the type of equipment, and the process and application.
  • the descaling composition will significantly reduce maintenance and operating costs.
  • the composition of the present invention is an excellent substitute for sandblasting. Following application, the present invention will result in white metal.
  • the composition does not damage seals, paints, gaskets, or thermal insulation.
  • the composition does not corrode the stainless steel, bronze or aluminum in treated equipment.
  • the composition was applied to the tower of a gas regenerating plant.
  • the design characteristics of the plant had a sour gas load of 525 MMcfd and a differential pressure of 88 mmHg.
  • the sour gas load was 380 MMcfd and the differential pressure was 116 mmHg.
  • the sour gas load this 500 MMcfd and the differential pressure was 57 mmHg.
  • This tower was cleaned with 9000 liters of the composition at a rate of 50 gallons per minute.
  • the required downtime was twelve days compared to the five days required for cleaning with the current composition. This resulted in a seven day savings of required time. As a result, there was enhanced productivity as a result of the present invention.
  • the composition was applied to a sweetening tower of a gas plant.
  • the sweetening tower had a design that had a sour gas load of 420 MMcfd and a differential pressure of 125 mmHg.
  • the sour gas load Prior to cleaning, was 325 MMcfd at a differential pressure of 182 mmHg.
  • the sour gas load was 451 MMcfd and the differential pressure was 188 mmHg. This was cleaned with 9000 liters of the composition. Once again, this exhibited a significant savings in the required time for cleaning, a significant reduction in production lost and a significant cost savings.
  • the gaskets of the absorber tower can be dirty. This is the reason why the tower's differential pressure is very high. Since the differential pressure is high, the design load could not be processed. After cleaning, the gasket recovered its design characteristics so as to correct the high differential pressure and tower channeling problems. The gaskets were returned to their entirely clean condition.
  • a cooler of a gas sweetening plant was treated with the composition.
  • the composition was applied to the lean amine plate coolers. These plate coolers were suffering from decreased efficiency.
  • the scaled plates showed an input temperature of MDEA a 100°C and water at 28°C.
  • the output temperature of the MDEA was 56°C and the water temperature was 45°C.
  • the MDEA input temperature was 100°C and the output temperature was 43°C. This was a 13°C differential as a result of the cleaning. This resulted in an estimated savings of 92% in the cost of plate cooler maintenance in comparison to the costs associated with other cleaning processes.
  • the present invention provides a composition that is biodegradable, operator friendly, and reusable.
  • the composition of the present invention reduces plant downtime by reducing cleaning downtime.
  • the composition of the present invention increases equipment productivity, when considering per day production, before and after the cleaning. Equipment maintenance costs are further significantly reduced. The equipment's useful life was significantly extended. This reduces the investment cost associated with new equipment and spare parts.
  • the composition of the present invention is also highly successful in association with external cleaning.
  • the paint on external surfaces is scaled with lime.
  • the composition of the present invention When the composition of the present invention is applied, it will fill pores and brighten the paint.
  • the composition is applicable on spheres, horizontal tanks and vertical tanks.
  • the savings in comparison with manual cleaning is significant.
  • the manual cleaning would take 45 days.
  • the cleaning can be carried out in two days.
  • the external cleaning can be carried out in association with flanges, elbows, valves, carbon filters, studs, along with liquid absorber tower rings and gaskets.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Zoology (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Un procédé de formation d'une composition de détartrage comprend les étapes consistant à : faire macérer une farine d'os dans une solution de diméthylamine ; faire digérer la farine d'os macérée avec de l'acide chlorhydrique ; neutraliser la farine d'os digérée avec de l'oxyde de calcium ; traiter la farine d'os neutralisée avec de l'acide sulfurique ; et appliquer un traitement de reflux avec de la diméthylamine et de l'hydrate d'hydrazine. Avant l'étape de digestion, le procédé comprend également les étapes consistant à : retirer les solides dans la farine d'os macérée de la solution de diméthylamine ; et transférer les solides retirés jusqu'à une tour d'extraction. L'acide chlorhydrique est mis en circulation dans la farine d'os macérée. La farine d'os traitée et l'acide sulfurique sont filtrés de manière à produire une phase liquide et une phase solide. La phase liquide contient une amine phosphate. La diméthylamine et l'hydrate d'hydrazine sont ajoutés à la phase liquide.
PCT/US2015/040628 2015-07-09 2015-07-15 Procédé de formation d'une composition de détartrage WO2017011010A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US2015/040628 WO2017011010A1 (fr) 2015-07-15 2015-07-15 Procédé de formation d'une composition de détartrage
US15/741,904 US10487298B2 (en) 2015-07-09 2015-07-15 Process for forming a descaling composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2015/040628 WO2017011010A1 (fr) 2015-07-15 2015-07-15 Procédé de formation d'une composition de détartrage

Publications (1)

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WO2017011010A1 true WO2017011010A1 (fr) 2017-01-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019188941A1 (fr) 2018-03-27 2019-10-03 日本製鉄株式会社 Système d'analyse, procédé d'analyse et programme

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1789805A (en) * 1929-02-16 1931-01-20 Passivation Products Company Chemical composition and metal-treatment process
US3374055A (en) * 1962-11-14 1968-03-19 Cie Des Gelatines Francaises Extraction of phosphoric acid and the purification thereof
US3686123A (en) * 1971-04-05 1972-08-22 Kurita Industrial Co Ltd Cleaning composition
WO1997044428A1 (fr) * 1996-05-21 1997-11-27 The Procter & Gamble Company Compositions de nettoyage acides
WO2011115302A1 (fr) * 2010-03-19 2011-09-22 味の素株式会社 Procédé pour la production d'acide phosphorique à partir d'os et procédé et dispositif pour l'emploi d'acide phosphorique produit à partir d'os dans la fermentation de sucre
CN104726876A (zh) * 2013-12-19 2015-06-24 苏燕敏 一种清洁锅炉的酸洗剂

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1789805A (en) * 1929-02-16 1931-01-20 Passivation Products Company Chemical composition and metal-treatment process
US3374055A (en) * 1962-11-14 1968-03-19 Cie Des Gelatines Francaises Extraction of phosphoric acid and the purification thereof
US3686123A (en) * 1971-04-05 1972-08-22 Kurita Industrial Co Ltd Cleaning composition
WO1997044428A1 (fr) * 1996-05-21 1997-11-27 The Procter & Gamble Company Compositions de nettoyage acides
WO2011115302A1 (fr) * 2010-03-19 2011-09-22 味の素株式会社 Procédé pour la production d'acide phosphorique à partir d'os et procédé et dispositif pour l'emploi d'acide phosphorique produit à partir d'os dans la fermentation de sucre
CN104726876A (zh) * 2013-12-19 2015-06-24 苏燕敏 一种清洁锅炉的酸洗剂

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019188941A1 (fr) 2018-03-27 2019-10-03 日本製鉄株式会社 Système d'analyse, procédé d'analyse et programme

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