US2203649A - Acid solution - Google Patents

Acid solution Download PDF

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Publication number
US2203649A
US2203649A US221009A US22100938A US2203649A US 2203649 A US2203649 A US 2203649A US 221009 A US221009 A US 221009A US 22100938 A US22100938 A US 22100938A US 2203649 A US2203649 A US 2203649A
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Prior art keywords
acid
90min
pickling
addition
acids
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Expired - Lifetime
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US221009A
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Felkers Pieter Frederik
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Stikstofbindingsindustrie "nederland" N V
STIKSTOFBINDINGSINDUSTRIE NEDE
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STIKSTOFBINDINGSINDUSTRIE NEDE
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F1/00—Tubular elements; Assemblies of tubular elements
    • F28F1/10—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses
    • F28F1/12—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element
    • F28F1/24—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely
    • F28F1/32—Tubular elements and assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with projections, with recesses the means being only outside the tubular element and extending transversely the means having portions engaging further tubular elements
    • 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
    • C11D7/34—Organic compounds containing sulfur
    • 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
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/065—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors sulfur-containing compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22D—PREHEATING, OR ACCUMULATING PREHEATED, FEED-WATER FOR STEAM GENERATION; FEED-WATER SUPPLY FOR STEAM GENERATION; CONTROLLING WATER LEVEL FOR STEAM GENERATION; AUXILIARY DEVICES FOR PROMOTING WATER CIRCULATION WITHIN STEAM BOILERS
    • F22D1/00—Feed-water heaters, i.e. economisers or like preheaters
    • F22D1/02—Feed-water heaters, i.e. economisers or like preheaters with water tubes arranged in the boiler furnace, fire tubes, or flue ways
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
    • F24H1/00—Water heaters, e.g. boilers, continuous-flow heaters or water-storage heaters
    • F24H1/10—Continuous-flow heaters, i.e. heaters in which heat is generated only while the water is flowing, e.g. with direct contact of the water with the heating medium
    • F24H1/12—Continuous-flow heaters, i.e. heaters in which heat is generated only while the water is flowing, e.g. with direct contact of the water with the heating medium in which the water is kept separate from the heating medium

Definitions

  • This invention relates to the art of pickling metals and more especially to means for improving the results obtained with acid pickling baths and for preventing the attack of metals by solutions of acid reaction.
  • metals and metal alloys are attacked by organic and inorganic acids in the presence of water and especially by aqueous solutions of acids.
  • aqueous solutions of acids or acid salts in order to remove scale and impurities on the surface of the treate me a s, not only the scale and impurities are removed; a certain amount of the metal also dissolves under the formation of metal-salts in the bath, involving a loss of active acid.
  • One object of the invention is to prevent or minimize the dissolution of metal during pickling and the loss of active acid.
  • Another object of the invention is to prevent the attack of metals by acidic solutions in chemical and physical processes wherein such acidic solutions are used in metallic receptacles.
  • Another object is to prevent or minimize the contamination of the air with acid particles originating from the bath and carried into the atmosphere by the hydrogen generated during the pickling treatment, the presence of acid particles in the atmosphere being noxious for the workmen.
  • Still another object in view is to prevent or minimize the occurrence of gas enclosures in the treated metallic object, such enclosures of gas occurring frequently after pickling processes and being probably due t5 the solution of hydrogen gas developed "by the process in the metallic surface.
  • a further object of the invention is to prevent or minimize the brittleness of the treated metal which is usually caused by pickling treatment, caused by the hydrogen in statu nascendi developed in the treatment.
  • compositions may be used for the purposes aforesaid, as will be described hereinafter.
  • a non-oxidizing acid solution is used with an addition of an inhibitor of the group constituted by the alkyl-thiocyanates and the aralkylthiocyanates.
  • aceticand oxalic acid may be successfully used.
  • a non-oxidizing mineral acid such as lphuric and hydrochloric acid
  • aqueous solutions of acid salts such as sggiium bis ulfa te may be profitably used.
  • Inhibitors which appeared to be useful according to this invention are e. g. methylthiocyanate, benzylthi dithiocyano-ethane (NCS-C Hz-SCN), and other alkylor aralkylthiocyanates.
  • the protecting action of the thiocyanate contained in the pickling baths can be improved by the addition of capillary active agents, such as wetting agents, and/or foaming agents and/or a er 1 1 o e composion.
  • capillary active agents such as wetting agents, and/or foaming agents and/or a er 1 1 o e composion.
  • ponine has been found to be a useful addition.
  • an inhibitor other than a thiocyanate for instance thiocarbanilide, appears to improve the inhibiting action of the thiocyanate and also the inhibiting action of the additional inhibitor.
  • the thiocyanates have been found to also improve the properties of protective coatings serving to prevent corrosion of metals.
  • the dimensions of the iron pieces were about 4.0 to 2.5 to 0.1 cm., their weight averaged 5-6 grams.
  • the pieces were immersed in the solutions and under the conditions mentioned in the examples.
  • Example 1 Example IX cid-. no! n01. Acid 1101?? 110i. Addition. 0.100gr.herylthiocy- .040 gr. benzylthioanate. cyanate. Tem erature 30C 39C 0.010 gr. benzyisul- Beac on time.. Addm 1L nde. Decrease oiweight 0.050 gr. Quimbin (a 1mpedingaction.. not made by V. Servo oi Delden, Holland) Emm le 11] Temperature 40C 40C.
  • Example X Temperature 39C 39C. geaction timelgfii ilzgfllin 90min.
  • Example V Acid E804... E801. Addition.-. 0.100gr. dithiocyanoethane. Temperature 78 C 78Q. Reaction time 90min..-. 90min. oiweight 77.5%--.” 0.650%. Impeding action .2%.
  • Example VII Acid mam--- msot' 0.0125 gri benzylthiocyana e. Adam 0.050gr.dithiocyanoethane. Temperature 78C 78 Q. Reactiontime 90min 90mm. Decreeseoiweight 77.6% -- 0.240%. Impeding action 09.7%.
  • the pickling bath of claim 1 in which the acid belongs to the group constituted by sulphuric and hydrochloric acids.
  • the pickling bath of claim 1. in which the acid belongs to the group constituted by acetic, citric and oxalic acids.
  • an aqueous solution containing a substance of the group constituted by non-oxidizing acids and acid salts, a substance of the group constituted by the aliqrlthiocyanates and the aralkylthiocyanates, with an addition of thiocarbanilide As a pickling bath, an aqueous solution containing a substance of the group constituted by non-oxidizing acids and acid salts, a substance of the group constituted by the aliqrlthiocyanates and the aralkylthiocyanates, with an addition of thiocarbanilide.

Description

Patented June 4, 1940 UNITED STATES PATENT OFFICE ACID SOLUTION Netherlands No Drawing. Application July 23, 1938, Serial 6 (flaims.
This invention relates to the art of pickling metals and more especially to means for improving the results obtained with acid pickling baths and for preventing the attack of metals by solutions of acid reaction.
It is well known that metals and metal alloys are attacked by organic and inorganic acids in the presence of water and especially by aqueous solutions of acids. In the pickling of metals with aqueous solutions of acids or acid salts, in order to remove scale and impurities on the surface of the treate me a s, not only the scale and impurities are removed; a certain amount of the metal also dissolves under the formation of metal-salts in the bath, involving a loss of active acid.
One object of the invention is to prevent or minimize the dissolution of metal during pickling and the loss of active acid.
Another object of the invention is to prevent the attack of metals by acidic solutions in chemical and physical processes wherein such acidic solutions are used in metallic receptacles.
Another object is to prevent or minimize the contamination of the air with acid particles originating from the bath and carried into the atmosphere by the hydrogen generated during the pickling treatment, the presence of acid particles in the atmosphere being noxious for the workmen.
Still another object in view is to prevent or minimize the occurrence of gas enclosures in the treated metallic object, such enclosures of gas occurring frequently after pickling processes and being probably due t5 the solution of hydrogen gas developed "by the process in the metallic surface.
A further object of the invention is to prevent or minimize the brittleness of the treated metal which is usually caused by pickling treatment, caused by the hydrogen in statu nascendi developed in the treatment.
Various compositions may be used for the purposes aforesaid, as will be described hereinafter.
According to the invention a non-oxidizing acid solution is used with an addition of an inhibitor of the group constituted by the alkyl-thiocyanates and the aralkylthiocyanates.
The addition of a small amount of these thiocyanates exerts a beneficial action on the pickling treatment and the above mentioned advantages are obtained when using an acid bath to which such compound is added.
In the Netherlands July 28, 1937 Organic non-oxidizing acids, such as formic,
aceticand oxalic acid may be successfully used. are rule it will however be preferable to use a non-oxidizing mineral acid such as lphuric and hydrochloric acid as the acid compound for the purpose in view, though other mineral or organic acids than those above mentioned and aqueous solutions of acid salts, such as sggiium bis ulfa te may be profitably used. Inhibitors, which appeared to be useful according to this invention are e. g. methylthiocyanate, benzylthi dithiocyano-ethane (NCS-C Hz-SCN), and other alkylor aralkylthiocyanates.
In certain cases the protecting action of the thiocyanate contained in the pickling baths can be improved by the addition of capillary active agents, such as wetting agents, and/or foaming agents and/or a er 1 1 o e composion. ponine has been found to be a useful addition.
The addition of an inhibitor other than a thiocyanate, for instance thiocarbanilide, appears to improve the inhibiting action of the thiocyanate and also the inhibiting action of the additional inhibitor.
The thiocyanates have been found to also improve the properties of protective coatings serving to prevent corrosion of metals.
As an illustration of the invention some examples are given hereunder, wherein the results of tests with small pieces of hoop-iron are given.
The examples serve to elucidate and clarify the invention; the invention is however not restricted to the compositions and compounding substances mentioned therein.
The dimensions of the iron pieces were about 4.0 to 2.5 to 0.1 cm., their weight averaged 5-6 grams. The pieces were immersed in the solutions and under the conditions mentioned in the examples.
In all examples 100 ccms. of a 20% acid were used.
Example I Acid HaBO4 HzSOa.
Additi n 0.033 gr. benzylthiocyanate.
Temperature 8P0 80 0. Reaction time... 90min.. 90min. Decreaseolweight 29.3%.... 0.07%. Impedingactmn 99.9%.
Example 1! Example IX cid-. no! n01. Acid 1101...... 110i. Addition. 0.100gr.herylthiocy- .040 gr. benzylthioanate. cyanate. Tem erature 30C 39C 0.010 gr. benzyisul- Beac on time.. Addm 1L nde. Decrease oiweight 0.050 gr. Quimbin (a 1mpedingaction.. not made by V. Servo oi Delden, Holland) Emm le 11] Temperature 40C 40C.
tion time Because of weight... Acid no HCL Impedmg 50mm 0.100 gr. benzylthio- Addition cyanate.
0.400gr.saponine. Example X Temperature 39C 39C. geaction timelgfii ilzgfllin 90min.
359% Acid. H;S04 HQSO HQBO. Impedina 993% Addition 0.025 gr. benzyl- 0.025;. Dr.Voge1s Beiz-Zusatz.
Temperature. 78 C.-. 78 0. Example IV Reactiontima 90min. 90min. 90min Decree a: 0i 56.Zl%.- 0.11% 27.7%
were Acid mach.-. mam. p ing ac 99.8% 50.7%. 0.100 gr. methylthioi .Addition cyanate. i 1 Th its d i hib ti 1 3 re 9 Superior resu an superior n i ng m ?3ihtij::::::::::::: $329.31: 3913?: effect obtained by the composition according to Impeding action this invention is illustrated by the comparative tests reproduced in the following table:
Table Acid HC] H01 HCI HG! H01 HCl. Addition 0.100% Rodinc 0.100% Rodine 0.100% Dr. vogei e 0.100% Ferrophil' 0.(K)%benzylthi(y 40. 41. Beiz-Zusatz. IZExtrem-Sparbeizcyanate.
u Temperature 43 C... 43C 43 (2.-.. Reactiontiine 90min. 90min 90min... Decrease of weight in 12.45..-. 3.10 3.02
percent. Impeding action in per- 75.1 75.7
cent.
1 Made by American Chemical Paint Co. Made by "Chemos" A. 0., Aussig, Csechosiovnkin.
Example V Acid E804... E801. Addition.-. 0.100gr. dithiocyanoethane. Temperature 78 C 78Q. Reaction time 90min..-. 90min. oiweight 77.5%--." 0.650%. Impeding action .2%.
Example VI Acid 38,804"... H2804. Addition 0.025 gr. benzylthlocyanate. Temperature 78 C. 78 q. Reaction time..... 90min. 00min. Decreaseoi weight 77.5%.. 0.171%. Impeding action 90.8%.
Example VII Acid mam--- msot' 0.0125 gri benzylthiocyana e. Adam 0.050gr.dithiocyanoethane. Temperature 78C 78 Q. Reactiontime 90min 90mm. Decreeseoiweight 77.6%..." 0.240%. Impeding action 09.7%.
Example VIII 7 Acid H01 H01.
0.070 gr. benzylthiocyanate. Addition 0.131110i gr. thiocarbane. 0.020 gr. saponine. Temperature 45C 45 C. Reactiontime 90min..- 90min. 'DecreaseQIWeighLHL 16.25% 0.00%.
Impedingaction 100.0%.
Various changes may be made in the details disclosed in the foregoing specification without departing from the invention or sacrificing the advantages thereof.
I claim:
1. As a new pickling bath, an aqueous solution containing a substance of the group constituted by non-oxidizing acids and non-oxidizing acid salts and a substance of the group constituted by the alkylthiocyanates and the aralkylthiocyanates.
,2. The pickling bath of claim 1, in which the acid belongs to the group constituted by sulphuric and hydrochloric acids.
3. The pickling bath of claim 1. in which the acid belongs to the group constituted by acetic, citric and oxalic acids.
4. The pickling bath of claim 1, in which the thiocyanate belongs to the group constituted by benzylthiocyanate, methylthiocyanate, dithiocyano-ethane.
5. As a pickling bath, an aqueous solution containing a substance of the group constituted by non-oxidizing acids and acid salts, a substance of the group constituted by the aliqrlthiocyanates and the aralkylthiocyanates, with an addition of thiocarbanilide.
6. The process which consists in pickling metal with an aqueous solution containing a substance of the group consisting of non-oxidizing acids and acid salts and a substance of the group consisting of the alkylthiocyanates and the aralkylthiocyanatcs.
PIE'I'ER FREDERIK FELKERS.
US221009A 1937-07-28 1938-07-23 Acid solution Expired - Lifetime US2203649A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425320A (en) * 1942-10-23 1947-08-12 Koppers Co Inc Cleaning and pickling of metals
US2459119A (en) * 1946-09-27 1949-01-11 Hooker Electrochemical Co Corrosion retarder
US2599729A (en) * 1947-08-26 1952-06-10 Detrex Corp Noncorrosive metal cleaning composition
US2617771A (en) * 1946-09-27 1952-11-11 Hooker Electrochemical Co Corrosion retarder
US2662857A (en) * 1948-03-26 1953-12-15 Pennsylvania Salt Mfg Co Pickling bath agent
US3003899A (en) * 1957-05-17 1961-10-10 Dow Chemical Co Removal of scale deposits
US3114657A (en) * 1960-08-29 1963-12-17 John W Stilwell Composition and method for cleaning and stripping metals
US3969255A (en) * 1974-04-01 1976-07-13 Connelly Jr George F Pipe cleaning composition
US4025359A (en) * 1974-04-01 1977-05-24 Connelly Jr George F Inhibited acid composition for cleaning water systems

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425320A (en) * 1942-10-23 1947-08-12 Koppers Co Inc Cleaning and pickling of metals
US2459119A (en) * 1946-09-27 1949-01-11 Hooker Electrochemical Co Corrosion retarder
US2617771A (en) * 1946-09-27 1952-11-11 Hooker Electrochemical Co Corrosion retarder
US2599729A (en) * 1947-08-26 1952-06-10 Detrex Corp Noncorrosive metal cleaning composition
US2662857A (en) * 1948-03-26 1953-12-15 Pennsylvania Salt Mfg Co Pickling bath agent
US3003899A (en) * 1957-05-17 1961-10-10 Dow Chemical Co Removal of scale deposits
US3114657A (en) * 1960-08-29 1963-12-17 John W Stilwell Composition and method for cleaning and stripping metals
US3969255A (en) * 1974-04-01 1976-07-13 Connelly Jr George F Pipe cleaning composition
US4025359A (en) * 1974-04-01 1977-05-24 Connelly Jr George F Inhibited acid composition for cleaning water systems

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Publication number Publication date
NL47784C (en)
NL83516C (en)
FR841279A (en) 1939-05-15

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