BE366437A - - Google Patents

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Publication number
BE366437A
BE366437A BE366437DA BE366437A BE 366437 A BE366437 A BE 366437A BE 366437D A BE366437D A BE 366437DA BE 366437 A BE366437 A BE 366437A
Authority
BE
Belgium
Prior art keywords
iron
acid
acids
hydrochloric
stannous
Prior art date
Application number
Other languages
French (fr)
Publication of BE366437A publication Critical patent/BE366437A/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors

Description

       

   <Desc/Clms Page number 1> 
 
 EMI1.1 
 procède de passive tien du fer et de ses congénères. 
 EMI1.2 
 



  La présente 'Invention e pour objet un procédé peur protéger le fer et ses c nJ=nres,c'est '' dire la fonte,la tô7e;l'acier et dents une cert9na mesu 'e le e fer blanc contre 7'a ticn corrc- sive des re16 ,s chicrhydricue- et sul furique de diverses concen- trti¯.ns ainsi cyu ds cLmp ses ou solutions qui en cotti panent. 



  En d'autres tr:r" ¯¯s, .;1 7 vise â rendre possible le transport, lE :;,?nu-t:int;1,n et 7= manioulation de ces acid;s dans des réci- oients 2D 1,1- st en :,ét.uY apparentés à celui-ci. 



  Il esi c'nr.u C" "ongle date qu'additionnés en petite quai- tité sux acides dilu2s,les sels de cuivre recouvrent temporaire- ment d'elle mince cc L.clle de cuivre métallique plus ou moins homo- gène et adhérente;') es objets de fer ou d'acier qu<on y plonge et minimis8ntâinsi la prise des acides sur le métal. Mais à mesure r:u'e1Je sugmente cette couche perd son adhérence peur devenir s,,), DZ:lCU;;e 1 l 'ettaque reprend de plus peJle. Les sel de cuivre n#i sont pas des Ipassiveurs efficaces. 

 <Desc/Clms Page number 2> 

 
 EMI2.1 
 



  Plus réels et plus durables,quoique cepend8Dt toujours in- complets, sont les effets des composés ars6nieu#:. On en tire prc- fit en tréfilerie où l'on ajoute un peu d'rrs::.nite de soude aux bains (sulfuriques) de décap,?.ge,réa7is:-nt 5nsi une importante économique d'acide et de métal,car dés que 1 a. ,'cuche d'oxyde a été dissoute,il se dépose sur le métal mis nu une mince pel- licule protectrice d'arsenic métallique, (ïette pratique est tolérable en tréfilerie o le travail est conduit sous la surveiJ- lance d'un ingénieur ou d'un contre-meitre intelligent et os d'ail''eurs la barre ,passant du brin de decspsge 1 eeIni de su''fa4 te de cuivre et ensuite à la fil ière est 8.1 rs-.i.tf"t désrrsÓniquée.

   on pourrait imaginer d'autres applications intéresssates de l'ac- tion passivante de l'arsenic, si la toxicité r3douteble de ce produit n'était un obstacle absolu son emploi en pntique cou- rante. Il existe d'ailleurs à ce sujet ;;ne 1 ,:,':isl ath'n rc:-rt 
 EMI2.2 
 stricte. 
 EMI2.3 
 



  Le procédé, objet de 1'invention ver::et de r snc1x'? ebsc 1 UY:1-')r,t nulle l'action des' acides chlorhyc1ricue'" et sui furi(jue cisscus sur le fer et ses congénères,tout en Évitant I es inconvénients et les dangers inhérents à l'emploi des ccmx,s:.as 81"s6nieux. Il est caractérisé par l'addition aux acides chlorhydrique et sulfu- riquelconcentrés'ou dilués ,ou eux solutions et produits cini en contiennent,de composés stanneux :''u stj,1,Ísnx:. 



  Si a 'une solution d'acide sul furiur;JQ8 -rc:i::len exempt d'acide nitrique,à 20 % v/v an ajoute une -.-'etite quantité dv sul- fate -Du de-chlorure stanneux et qu,cn y plonge une leme d' c e? ; celle-ci ne dégage pas la moindre bulle e ci'iijcôrc;1>ne r8irt;léJtrice d'une attaque si.minime scit-eJJe,dn mste.l. On vcitJ8u ccntr%5.-=e, 1 loxyde bleu - écaille de laminoir - se dissoudre et 13 rnétel mis 1 hm présenter une belle surface d'un ble,ne srS'3J'it. rI en 
 EMI2.4 
 est encore de même lorsqu'on ajoute un oeu de chlorure stanneux 
 EMI2.5 
 t une solution obtenue en diluant une q1i:nU.tj d.-nnée d'ecic1e chlorhydrique (blanc de préférence) avec 3 cu 4 fois son volume d'eau. t'attaque est absolument nu' 1.

   El 1 devient réelle, au contraire, quoique déjà. affaiblie,lorC1U,r'J:1 Îlc-r'3e une lane d'acier 

 <Desc/Clms Page number 3> 

 
 EMI3.1 
 dbns lucide ci7c¯rh,driçue Î 20 Q Bé additionné de chlorure stenneux. M#.iY il n'en est pi1-s de mme lorsqu'au chlorure stsnr.eux en sr--,stitt.e le s21 stibieux correspondant. D3ns ce c:s ,8ns ,.L,'i' a'c'-:l':j,3s2 i moindre bulle c1'h;ydrogèoe,on voit le c, UCh2 d-./n sc dissoudre rapidement et Da a 1 iqueur se f sn-7ir 68 nlo  jes 6.'un brun v;;"dàtre,tandis que bientêt le mé- tel >.i . P I1G L ::'n it d'un beéu blanc. Au bout de que7ques heures 1 =.; na ,:..8 z# c:i::si¯ent;7 liqueur s'éclaircit et le r,o;tcl :r.,nLi cd) ...ct \.0 p,--u .:risS,tre. La lame peut rester lu: ':'3 Cc: 1,,; cet ::(;::':.<8 J-ôm ent des semaines sans être le e mcins du !11.nr.J.''; z ¯¯ ¯.

   Il en est de ra@rfje ,à plus forte rss'n;]orsqu' un ci ': , Li C'; 1,. c: ,( " ;- l :' t:' e ent . c.,:# )l'jr:,'; ',,,8 très S'[LL1.:;s,ci8 Ja passivation du fer et de ses c-.t1/..:d:,r:s nit s;..oecz :ti& 1 es d'une infinité d'applications Jr, ti cu -,8. 



  A titr ci' ,,:,:,.:-,19 (n n ci tr2 notamment les applications sui- v,' r;t2s : 1) L'c'uiT'n de c 'ú)Ls6s sta'nne';x ou stibieux aux ccmbin27 sc n s ' -L,.2,: m ''-eic-e 2U' furi',ue(bi et tetra ou pclysulfates ?iea.4 lins) en c'urs (L fvbr-ic: t.mn lorsqu'elles sont Il J'état liqui- 
 EMI3.2 
 de (au-dessus Je 100 6) da manière à obtenir lors du rfrcic5isp5 S8ÏDent,ü.:s :-A'''''-6''''",,;;; ,r, duits s: 7 ides susceptibl es,gr2c à 1 'Lde:ic':',--'n des jJi,sr-1.v.,irs indiqués ci-dessus,d'être ema7lés et cns3rvs " nô, :ïi;:1:.;.;nt aans 1Jies tambours en fer en vue de leur t<t:1." i..> ti.. s:tri¯:ure peur lépG.ndage d'une sclution dilu- ée d'#:->-1,ù.e 81. ' furlc\e sur es champs, en vue de 1 a destruction des >sJ1J.v:.E . e: .,':l'bes.

   Cette ac >7 icaticn permet notamment de se servir, ,1<.; r 1 'ép;lù:;ge de 7 a sc,luticn &-'aeiô.e,d' épa,nd<eurs en fer,peu coûteux st de c r.structicn ordinaire au lieu de pu]- vérisat-jurs n::Y :ux er; cuivre pic-mbé ou en plomb antimc.nié,tels qu'en use:::s Ectr,êô"le1ent. 



  2) 7'adctiticn d3 c:-l.r. n;re stibieux à l'acide chlorhydrique du commerce â 19/21 Bé en vue de permettre son expédition dans des tonneaux ou des ej.fernes en fer, en remplacement des touries ou 

 <Desc/Clms Page number 4> 

 
 EMI4.1 
 bonbonnes ou: encore des jarres en grés 7i-,,. des citernes ébcnitées 
 EMI4.2 
 auxquelles* on devait recourir jusqu'ici. 
 EMI4.3 
 3) 'L'addition d'un des agents indiqués à de l'acide chlorhyd,ri- 
 EMI4.4 
 que dilué en.vue de permettre son application au détartrage des 
 EMI4.5 
 -chaudières et tuyaux de canelisations, applicatic'n rendue possible 
 EMI4.6 
 par ce fait que.cet acide ainsi "corrigé" n'attaque plus du tc.ut 
 EMI4.7 
 la 'tôle ni 1 'aci er. 
 EMI4.8 
 



  RESUME. 



  L'invention a pour objet : 
 EMI4.9 
 1) Le procédé pour protéger le fer et ses ccngénsres (la fontes ''' i'b. t81e,l'àeier et le fer blanc) sontre 11--cticn corresive des acides chlorhydrique et su1 furicsue, ainsi que des composes ou solutions qui en contiennent,ce }JY(.cé é c'tcnt caractérisé par l'addition a ces acides de ccnposôs stpn.-'u. 17 sti1)j,ux. 



  2) Une .forme.d'exécuticn du procède mentj'.''rn3 sr,us 1) esraetéi"1 sée par'l'addition des composés stanneux c:u stibieux aux 1:1i et tétra-,ou ¯polysulfates alcalins en cr.urs de afin de 
 EMI4.10 
 s permettre leur emballage et leur conservation dans des récipient 
 EMI4.11 
 en'fer'en vue de leur utilisation li.1 tér erre pour 1 
 EMI4.12 
 d'acide sulfurique dilué en agriculture. 
 EMI4.13 
 



  03)1 Une'forme d,exéeu.tion du prccëdô menti'-nnô S(.us 1) carec- térisée par l'addition de chlorure àiilJ5 eu>1 de 7'acide calorhydrique concentré ou de chlorure G-LibL=-u7, ,u stanneux de l '4 acide chlorhydrique étendu en vue de permettre 1 iex.-)6ditîGn de 
 EMI4.14 
 cet- acide dans des tonneaux ou citernes en fer et son applica- 
 EMI4.15 
 tion au détartrage des chaudières et c.n.,istirrs. 



  4) Les produits obtenus par 7 es précédés mentionnés sons su 3 n'attaquant pas le fer et ses congénères ;ces pre. duits étant caractérisés par des acides chlcrliyôri*,¯u, eu s1=F furique;c,1a des composés'ou solutions qui en cC'nti,:rment, l3c1cïi ticnnés de ccnpo- sués stanneux ou stibi6ux-.



   <Desc / Clms Page number 1>
 
 EMI1.1
 proceeds from passive ownership of iron and its congeners.
 EMI1.2
 



  The object of the present invention is a process to protect iron and its cnJ = nres, that is to say cast iron, sheet metal; steel and teeth a certain measure of tinplate against 7'a Corrective ticn of re16, hydrochloric acid and sulphuric acid of various concentrations, thus cyu ds cLmp its or solutions which cotti panent.



  In other words tr: r "¯¯s,.; 1 7 aims to make transport possible, lE:;,? Nu-t: int; 1, n and 7 = handling of these acids in containers 2D elements 1,1- st in:, ét.uY related to this one.



  It is also the case that, added in small quantities to dilute acids, the copper salts temporarily cover it with a thin layer of more or less homogeneous metallic copper and adherent; ') objects of iron or steel that are immersed in them and thus minimize the setting of acids on the metal. But as r: u'e1 I increase this layer loses its adhesion to become s ,,), DZ: lCU ;; e 1 the attack resumes more and more. Copper salts are not effective passivators.

 <Desc / Clms Page number 2>

 
 EMI2.1
 



  More real and more lasting, though still incomplete, are the effects of arsenieu #: compounds. It is obtained from it in a wire-drawing factory where a little soda is added to the pickling (sulfuric) baths,?. Ge, réa7is: -nsi a significant economic acid and metal , because as soon as 1 a. The oxide layer has been dissolved, a thin protective film of metallic arsenic is deposited on the exposed metal, (this practice is tolerable in wire drawing where the work is carried out under the supervision of an engineer. or an intelligent countermeter and bones elsewhere the bar, passing from the strand of decspsge 1 eeIni of copper su''fa4 te and then to the die is 8.1 rs-.i.tf "t DesrrsÓnicated.

   one could imagine other interesting applications of the passivating action of arsenic, if the dreadful toxicity of this product were not an absolute obstacle to its use in current medicine. There is also on this subject ;; ne 1,:, ': isl ath'n rc: -rt
 EMI2.2
 strict.
 EMI2.3
 



  The method, object of the invention ver :: and r snc1x '? ebsc 1 UY: 1 - ') r, t null the action of' hydrochloric acids' "and sui furi (jue cisscus on iron and its congeners, while avoiding the drawbacks and dangers inherent in the use of ccmx , s: .as 81 "s6nieux. It is characterized by the addition to hydrochloric and sulfuric acids concentrated or diluted, or their solutions and products containing it, of stannous compounds:" u stj, 1, Ísnx :.



  If to a solution of sul furiur acid; JQ8 -rc: i :: len free of nitric acid, at 20% v / v an add a -.- 'small amount of sulphate -Du de-stannous chloride and that, cn plunges a leme of this? ; this does not release the slightest bubble e ci'iijcôrc; 1> does not result in an attack so.minime scit-eJJe, dn mste.l. We live with ccntr% 5 .- = e, 1 blue oxide - rolling mill scale - dissolve and 13 rnétel put 1 hm present a beautiful surface of a wheat, not sure. nothing
 EMI2.4
 is still the same when adding an egg of stannous chloride
 EMI2.5
 t a solution obtained by diluting one q1i: nU.tj d.-nno of hydrochloric water (preferably white) with 3 cu 4 times its volume of water. you attack is absolutely naked '1.

   El 1 becomes real, on the contrary, although already. weakened, lorC1U, r'J: 1 Îlc-r'3e a steel lane

 <Desc / Clms Page number 3>

 
 EMI3.1
 dbns lucid ci7c¯rh, driçue Î 20 Q Bé with the addition of stennous chloride. M # .iY it is not the same when with stsnr.eux chloride in sr -, stitt.e the corresponding stibious s21. D3ns ce c: s, 8ns, .L, 'i' a'c '-: l': j, 3s2 i lesser bubble c1'h; ydrogèoe, we see the c, UCh2 d-./n sc dissolve quickly and Da a 1 iqueur f sn-7ir 68 nlo jes 6.'un brown v ;; "dàtre, while soon the metal> .i. P I1G L :: 'n it of a white beéu. of a few hours 1 = .; na,: .. 8 z # c: i :: sīent; 7 liquor clears up and the r, o; tcl: r., nLi cd) ... ct \ .0 p, - u.: risS, tre. The slide can remain read: ':' 3 Cc: 1 ,,; ce :: (; :: ':. <8 J-ome weeks without being the th mcins du! 11.nr.J. ''; z ¯¯ ¯.

   It is the case of ra @ rfje, with stronger rss'n;] when a ci ':, Li C'; 1 ,. c:, ("; - l: 't:' e ent. c.,: #) l'jr :, ';' ,,, 8 very S '[LL1.:; s, ci8 Ja passivation of iron and of its c-.t1 / ..: d:, r: s nit s; .. oecz: ti & 1 es of an infinity of applications Jr, ti cu -, 8.



  A titr ci ',,:,:,.: -, 19 (nn ci tr2 in particular the following applications,' r; t2s: 1) L'c'uiT'n de c 'ú) Ls6s sta'nne' ; x or stibious with ccmbin27 sc n s' -L, .2 ,: m '' -eic-e 2U 'furi', ue (bi and tetra or pclysulfates? iea.4 lins) in hearts (L fvbr- ic: t.mn when they are He I state liquidi-
 EMI3.2
 of (above I 100 6) so as to obtain when rfrcic5isp5 S8ÏDent, ü.: s: -A '' '' '- 6' '' '",, ;;;, r, duits s: 7 ides susceptible, gr2c to 1 'Lde: ic': ', -' n of the jJi, sr-1.v., irs indicated above, to be ema7lés and cns3rvs "nô,: ïi;: 1 :. ;.; nt aans 1Jies iron drums in view of their t <t: 1. "i ..> ti .. s: trī: ure for the épG.ndage of a diluted sclution of #: -> -1, ù.e 81. 'furlc \ e on the fields, with a view to 1 a destruction of> sJ1J.v: .E. E:.,': L'bes.

   This ac> 7 icaticn makes it possible in particular to use,, 1 <.; r 1 ép; lù:; age of 7 a sc, luticn & - 'aeiô.e, of shoulder, nd <eurs in iron, inexpensive st of ordinary c r.structicn instead of pu] - Vérisat-Jurs n :: Y: ux er; pic-mbé copper or antimcnied lead, such as in use ::: s Ectr, êô "le1ent.



  2) 7'adctiticn d3 c: -l.r. n; re stibious with commercial hydrochloric acid â 19/21 Bé in order to allow its shipment in barrels or iron barrels, replacing carboys or

 <Desc / Clms Page number 4>

 
 EMI4.1
 carboys or: more earthenware jars 7i - ,,. ebcnite cisterns
 EMI4.2
 which we had to resort to until now.
 EMI4.3
 3) 'The addition of one of the agents indicated to hydrochloric acid, ri-
 EMI4.4
 than diluted in order to allow its application to descaling
 EMI4.5
 - boilers and pipes, applicatic'n made possible
 EMI4.6
 by this fact that this acid thus "corrected" no longer attacks tc.ut
 EMI4.7
 neither the sheet nor the steel.
 EMI4.8
 



  ABSTRACT.



  The subject of the invention is:
 EMI4.9
 1) The process for protecting iron and its constituents (cast iron, iron and tinplate) is 11 - cticn corresive from hydrochloric and su1 furic acids, as well as compounds or solutions which contain it, this} JY (.cé é c'tcnt characterized by the addition to these acids of ccnposôs stpn .- 'u. 17 sti1) j, ux.



  2) A .form.d'execution of the process mentj '.' 'Rn3 sr, us 1) spelled out by the addition of the stannous compounds c: u stibious to the 1: 1i and tetra-, or ¯polysulphates alkali in credit in order to
 EMI4.10
 s allow them to be packaged and stored in containers
 EMI4.11
 hell for their free use. 1 earth for 1
 EMI4.12
 dilute sulfuric acid in agriculture.
 EMI4.13
 



  03) 1 A form of exéeu.tion of prccëdô menti'-nnô S (.us 1) characterized by the addition of chloride to iilJ5 eu> 1 of 7'concentrated calorhydic acid or of chloride G-LibL = - u7,, u stannous 4 hydrochloric acid extended to allow 1 iex .-) 6ditîGn of
 EMI4.14
 this acid in iron barrels or cisterns and its application
 EMI4.15
 tion to the descaling of boilers and c.n., istirrs.



  4) The products obtained by the 7 mentioned precedents are su 3 which do not attack iron and its congeners; these pre. products being characterized by acids chlcrliyôri *, ¯u, eu s1 = F furic; c, 1a compounds' or solutions which in cC'nti,: rment, l3c1cïi ticnnes of stannous or stibi6ux- conposides.


    
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0169651A2 (en) * 1984-06-21 1986-01-29 Halliburton Company Method and composition for protecting metal surfaces from oxidative environments

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0169651A2 (en) * 1984-06-21 1986-01-29 Halliburton Company Method and composition for protecting metal surfaces from oxidative environments
EP0169651A3 (en) * 1984-06-21 1988-04-27 Halliburton Company Method and composition for protecting metal surfaces from oxidative environments

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