‘US006250314B1 United States Patent «2 10) Patent No: US 6,250,314 BL Wasserbauer et al. (45) Date of Patent: Jun. 26, 2001 (51) PROCESS OF PICKLING STAINLESS STEEL S847 + 191992 Bowsqet ta 143 (25) toventars: Brigitta Wasserbauer, Vienna; Fagor Shans34 + 121997 Rola ca iat Braun, Wie-Roclsun Geral 5785589 71058 Grand ca “ess Maresch, Médling, all of (AT) 5,804,056 9/1998 Pempera ct al. 205/661. (73) Assignee: Andrit-Patentverwaltungs-Geselschaft aie cremate las m.bH., Graz (AT) 51876522 3/1900 Figge eta. Lasisas " Samaes Uio90 Mekevtu ea 133 (7) Notice: Subject any dscaimes the term ofthis Soy Se Mag. MER aes paleat is extended or adjusted under 35. «S908 + 1199) umd ea sa USC. I54(o) by 0 days FOREIGN PATENT DOCUMENTS (21) Appl. No 092353776 s7asst + 2000 (DE) (22) Fil: Ju 15, 1999 + cited by examiner 0) Foreign Application Priority Data Primary Examiner—Sharidan Carrillo 1a 15,1968 (a0) ta17e8 (4) Aitorey, Agent, or Firm—Roslance, Abrams, Berdo (1) In. cl” 236 yoo © Goodman, LLP. (2) US.CL Ba; 134; 3415, 6) ABSTRACT ‘Suey 134385 P8439, 134 50, 3325 . sauce 1s SE 2S: 15428 1/80 13432: process and apparatus fr pickling the surface of snes , : Stel strip feeds he sonkes steel stip throuh a porality of (58) Fleld of Search 1 pickling tanks containing a hydrochloric acid pickling acid. 13428, 25,30, 33,36, 4,41, The pickling nid bath is mantined at a teroperature ofa s ferences Cite least about 40° C.An oxidizing agent added 10 the acid 6) aa a solution in an amount to maintain at least about one thitd and US. PATENT DOCUMENTS preferably a Feast abut bal ofthe soluble iron inthe form Pe ee enannen sean iene ned he alamo he 3928320 * 121975 Gnie 423135 30H solution SSon2se + toms Tut eal 143 ‘tarress | 2196) Crime ct a ideere 25 Claims, 3 Drawing Sheets 18 2a 12 4 1824 aa a MJ &U.S. Patent Jun, 26, 2001 Sheet 1 of 3 US 6,250,314 B1 FIG. 1 t 28 24 18 12 28U.S. Patent Jun, 26, 2001 Sheet 2 of 3 US 6,250,314 B1 AISI 409, 80 °C 12 1 08 06 04 0,2 0! + + 1 2 3 4 FIG. 2 AISI 409, 90 °C 12 1 08) 06: 0,4) 0,2) 0 + + 5 6 7 8 FIG. 3 AISI 409, 80 °C 0 10 20 30 40 50 % Perchloric Acid FIG. 4U.S. Patent Jun, 26, 2001 Sheet 3 of 3 US 6,250,314 B1 AISI 430, 80 °C AISI 304, 80 °CUS 6,250,314 BL 1 PROCESS OF PICKLING STAINLESS STEEL, FIELD OF THE INVENTION ‘The present invention is directed to process a pickling stainless steel. More pasticulaly, the invention ix directed to « process for pickling stainless steel in an acid bath, BACKGROUND OF THE INVENTION The process of pickling carbon steel with hydrochloric seid has established itself world-wide over the past few years as an elective pickling process and is use! in virtually all countries and steel works. In stainless steel pickling, however, there was always the technical belief that conven= tional stel pickling methods could not be used for stainless steel because of the different levels and type of scale formation on stainless steel. Surprisingly, however, it was ‘showin that a pickling elfect most certainly could be achieved with hydrochloric. acid. However, the pickling. times requited to oblain a seale-ftee surface on stainless stee] using hydrochloric acid ate very long compared with carbon steel. A'steel strip of grade St 12, for example, is pickled over a maximum of 30 seconds at 80° C, whereas a ‘comparable strip of grade AISI 409 stainless steel takes up to 10 minutes at 90° C. These extcemely long pickling times for stainless stee] using hydrochloric acid are unsuitable for practical operations because the number and length of tanks ‘eeded for pickling would be too great During the formation of stainless steel sheet products, 2 layer of scale is typically produced on the surface ofthe steel sheet, The scale must be removed, typically by pickling, before the steel can be used or further processed. Many stainless stel pickling baths use a mixture of hydrofluoric acid and nitric acid. ‘The mixture of these acids causes fumerous problems associated by the sludge formation of | these acids in the tanks. In addition, acid pickling of stainless ‘steel by the conventional process is a very slow provess and requites complex treating baths to provide adequate reten- tion time of the stainless steel in the acid bath, The sequen- pickling steps result in increased operating cost Accordingly, there is a continuing need in the industry for improved melhoxls of pickling stainless stec. ‘SUMMARY OP THE INVENTION “The present invention is directed to a process and appa ratus for pickling stailess steel. More pactculaey, the inveatioa is directed to continuous process for pickling a ‘continuous strip of stainless see ins hydrochlori acid bath in an efficient and economical fashion Accordingly, a primary aspect of the invention is to provide a process and apparatus for efliciently. pickling Stainless steel in an acid bath with reduced pickling times ‘compared to prior processes, “Another object ofthe invention is to provide a process and apparatus for pickling stainless stee] in a hydrochloric acid solution where the solution contains an oxidant. “Anoiher object ofthe invention is to provide a process and apparatus for pickling stainless stee] in a hydrochloric acid ‘olution where an oxidant isalded to the acid to oxidize at Jeast a portion ofthe dissolved iron to ferric chloride “Another object ofthe invention is to provide a process and apparatus for picking stainless steel in an aqueous hydro- cchioric acid solution where an oxidant is added to the hydrochloric acid solution in an amount based on the cealeulated dissolved iron content in the acid solution, ‘Sil another abject ofthe invention i to provide a process and apparatus for pickling stainless steel in an aqueous 0 3s 2 hydrochloric acid solution where at least one third of the soluble iron content in the aeid solution i present in the form of ferric chloride. Another object of the present invention is to provide a process. and apparatus for pickling stainless steel in an aqueous hydrochloric acid solution where at least one half of| the soluble icon content in the acid solution is present in the form of ferric chloride. ‘Afurther object of the invention isto provide a process for pickling stainless steel in an aqueous hydrochloric acid solution at a temperature of at least 40° C. ‘Afurther object of the invention isto provide a process foe pickling stainless steel in an aqueous hydrochloric acid Solution ata temperature at or below the boiling point of an aueotropie bydrochlorie acid solution. ‘Another object of the invention isto provide a process of pickling stainless steel in an aqueous hydrochloric acid ‘Solution where the ferric chloride content in the acid solution is measured and an oxidant is addled to the solution in an Amount based on the measured Fert chloride content Stil another abject of the invention is to provide a process and apparatus for pickling slainless steel in an aqueous hiylrochlorie acid solution where an oxidant is added tothe solution in an amount based on the weight or surface azca of the stainless steel stip being pickled "The objects of the invention are basically obtained by providing a process for pickling stainless steel comprising the steps of feeding a stainless steel artile into a bath of an aqueous hydrochloric acid solution and continuously adding an oxidant to the hydroeblorie acid solution in an amount in proportion tothe surface area tothe stainless steel article 10 ‘maintain at leas about one third ofthe dissolved ion content as ferric chloride. The objects of the invention are further obtained by providing @ process for pickling a stainless steel sti ‘comprising the steps of providing « plurality of pickling tanks arranged in series where each tank contains an aque ‘ous hydrochloric acid solution, feeding a continuous stat Jess sce trp through the hycrochlorie acid sofution in each ‘of said tanks to pickle the surface ofthe strip, and continu ‘ously adding an oxidant to the hydrochloric seid solution in ‘each ofthe tanks in an amount to oxidize Fe°“to Fe°*and to ‘maintain a ferric chloride content of atleast about one thie based on the total dissolved iron conteat of the acid solution. Other objects, advantages and salient features of the invention will become apparent from the Following detailed ‘description which in conjunction with the annexed drawings disclose a prefeered embodiment of the present invention, BRIEF DESCRIPTION OF THE DRAWINGS ‘The following isa brief description ofthe drawings which form a part of this original disclosure, in whiek: FIG. 1 is a schematic diagram of a pickling tank for pickling a stainless steel stip; FIG, 2 is a graph showing the comparative pickling time ‘of stainless steel by the addition of an oxidant to the acid solution at a temperature of 80° C3 FIG. 3 is graph showing the comparative pickling time ‘ofa stainless steel strip wih the addition of an oxidant ata temperature of 90° Cy FIG, 4 a graph shoving the comparative pickling times ‘ofa stainless steel strip with the addition of perchloric acid; FIG. Sis a graph showing the comparative pickling times (of AISI 430 stainless stel at 80° C5 andUS 6,250,314 BL 3 FIG. 6 isa graph showing the comparative pickling times ‘of AISI 304 stainless steel at 80° C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS “The present invention is directed to process and appa satus for pickling stainless steel. More particularly, the fnveation is diected to & process for pickling stainless see! jn a bath of a hydrochloric acid solution with reduced Dieklig times ‘The process of the invention uses a hydrochloric acid solution for pickling stainless tel ina manner to reduce the Pickling time about 50% compared to the prior stainless Sec aid pickling processes. The hydrachlori aid soliton ‘contacts the slainkssstel to predic ferrous chloride and fecrc chloride in the acid solution. The iaveation i directed toa process of adding an oxidizing agent tothe hydrochloric ‘cd solution io an amount to oxidize the Ferrous chloride 10 fear chloride. Oxidizing the soluble iron to fenti chloride hasbeen found to reduce the piling time for stainless steel 238 much as 50% compared to the prior ace pickling soht~ tions used for stainless set ‘The oxidizing agent is added to the hydrochloric acid solution ia the picking tank ia an amouat to attain the desired recction in pickling time. In_preferced ‘embodiments, the oxidizing agent is added tothe bydeo- chlor acid solution ia an amount to oxidize the fercous chloride to ferric cblride where atleast shout one thi of the soluble toa content in solution is present as fetic chloride based on the otal weigh of the soluble iron content in solution. Thus, the Fe*" concentration inthe acid solution 5 at least one thd of the combined weight ofthe Fe*"and Fe* In further embodimens, the oxidizing agent is added jn an amount lo maintain a ferric chloride content of atleast ahout 50% by weight based oo the total amount of the Soluble ion inthe acd solution In embodiments of the invention, the amount of the oxitizing agent is calelated and added to the pickling acid based on the surface area of the stainless steel being treated in the acid bath to maintain at least aboot one third of the soluble iron content as ferric chloride based on the total ‘mount ofthe soluble ioe in the seid solution. The feed rate and dimensions of the slanless lee) sirip and the acid ‘concentration ae used fo ealelate the acid consumption and formati of ion salts, and particulary the fen chloride ‘concentration inthe acid Solution. The amount of the oxi izing agent is ade in an amount based on the surface area ‘ofthe sce 0 attain the target percent of Fe™. Alternatively, the oxidizing agent ean be added in proportion tothe weight ‘ofthe stainless stel being teated by the acid solution. The ‘mount of the oxidizing agent is hased on theoretical cal= ‘ulations of the acid consumption and the Toemation of ‘Soluble ron sls based on the average surface area or Weight ‘ofthe stainless steel strip being tated The oxidizing aget canbe any suitable oxidizing agent capable of oxidizing Feo Fees known in the at Examples of suitable oxidizing agents include for example nitric aed, chlorine, hydrogen peroxide and chlorine hycro- {ea compounds Other suiable oxidizing agents include Sci containing chlorine, such as percblori aid, ebromium ‘oxygen compounds, sich as chromium oxide (CrO.), and fercic chloride. “The hydochlorc acid solution is typically & concentrated hydrochloric acid baving a pif of about 10, In preferred embodiments the hydrochloric acd solution isan azcotropie hydrochloric acid solution such thatthe act eoncentration m 3s 4 in the vapor phase is substantially the same as the acid Solution in the pickling anks. An acid concentration greater than an azcotropie mixture results in a high acid concentri- ton in the exhust fumes which must be removed prior 0 discharging the fumes to the atmosphere. The hydrechlorie acid solution is maintained at a temperature of at least about 40° C. cluring the pickling process of the stainless steel, In further embodiments, the hydrochloric acid solution is mai tained at a temperature at or below the boiling point of an aveotropie hydrochloric acid solution. ‘The ferric chloride content of the acid pickling solution is determined using standard techniques. For example, in ‘embodiments of the invention, the ferric chloride conteat of the aed solution is determined by measuring the density of| the solution, measuring the conductivity or oxidation reduc- tion potential of the solution by photometric measurements and combinations of these methods, Preferably, the ferric ‘chloride content i maintained within a predetermined range and the oxidizing agent is added to the hydrochloric acid Solution based of the measured ferric chloride content to ‘maintain the ferric chloride content within the desired range. The rate ancl amount ofthe oxidizing agent added tothe acid solution ean be adjusted in response to the rate of pickling as determined by the measured fervie chloride or fers ion ‘content of the acid solution, Thus, the oxidizing agent is added to the hydrochloric acid solution in an amount to ‘maintain the measured ferric chloride content at about one third based on the total ion content and solution. In furlher ‘embodiments, the oxidizing agent is added to maintain about ‘one half ofthe soluble iron as Ferrie chloride Referring to FIG. 1, » continuous pickling apparatus is illustrated for use in the process of the present invention. The apparatus as shown includes pickling tanks 12, 14 and 16 ‘connected in series. Each ofthe pickling tanks include feed rollers 18 at the inlet ends 20 for feeding a contiauous strip ‘of stainless steel 22 through the tanks, Discharge rollers 24 are positioned at the outlet end 26 of the tanks to guide the stainless steel strip 22 and support the stip in the hydro- ‘chlric acd solution 28. Fresh hydrochloric acid is generally ‘supplied to the downstream tank 16 with respect to the feed dizcetion ofthe stainless steel stip 22. The acid lows into the tank 16 and overflows or is pumped into the adjacent upstream tank 14. The acid in tank 14 is similarly pumped into the upstream tank 12. The stainless stel srip is feed into the frst pickling tank 12 and is carried sequentially through tbe tanks 14 and 16. The bydrochlorie acid removes the scale from the stainless steel to form ferrous chloride and ferrie chloride salts in the acid solution. The soluble iron ‘content in the acid in the upstream tank 12 is generally the highest wit the iron content decreasing i concentration in tanks 14 and 16, respectively ‘The acid solution 28 in preferred embodiments of the invention is an azeottopic hydrochloric acid solution. An szeotropic hydrochloric acid solution is desirable to prevent the eseape of high concentrations of hydrogen chloride in the exhaust gases, The acid solution in each of the tanks 12, 14 and 16 is ‘circulated through a pipe 30 from the upstream end of the tank and is earied by a pump 32 to a recirculation tank 34 where the acid is regenerated or replenished with fresh aed. ‘The acid from the eigculation tank 34 is pumped through a pipe 36 and recycled to the discharge end of the respective Pickling tank ‘The oxidizing agent can be added to the hydrochloric ac in solid form as 8 powder. Alternatively, the oxidizing agent ‘ean be added as & gas or as an aqueous solution. GenerallyUS 6,250,314 BL 5 a powdered or gascous oxidizing agent is more preferred to avoid diluting te pickling cid with the solvent. In preferred ‘embodiments, the oxidizing agent can be supplied t0 the pipe 30 upsiream ofthe pump 32 such thatthe suction athe inlet ofthe pump 32 craws the oxidizing agent into the acid solution and cartes the mixture to the reitcuatin tank 34 ‘The oxidizing agent and the spent acid withdrawn from the Pickling tanks are mised in the reciculation tank 34 10 ‘oxidize the ferous chloride to ferric chloride which then retuned t0 the pickling tank. Alternatively, the oxidizing agent can be fed diteeily into the recitculating tank 34 through a pipe 40. Alternatively, the oxidizing agent can be supplied directly to a separate feed inlet ofthe pump 32 or supplied with the fresh seid directly into the pickling tank ‘Ameasring device 42 is provided in each ofthe piling tanks to eootinvousty monitor and measure the ferric chlo- ride concentration of the acid solution. The measuring ‘device can be conventional device capable of continuously monitoring the Fe"eoneentration. In further embodiments, the measuring deviee ean determine the Fe*concentration at predetermined intervals, The measured ferric chloride con- ‘eotration is used as a bass to determine the feed rate and the amount ofthe oxidizing agent added to the hydrochloric acid solution, The measuring deviee can be coupled 10 & metering devie (not shown) for feeding aod controling the amount ofthe oxidizing ageot aed to the hydrochloric acid solution. In preferred embodiments of the invention, the ‘oxidizing agent inadded continuously withthe circulation of the spent pickling acid to maintain a substantially constant fers chloride acid solution and to prevent the feric eblo- ide concentration from falling below the threshold value Generally, the oxidizing agent is eoatinuousiy added 10 the acid solution to maintain atleast one tied and preferably at Jeast one half of the soluble iron content in the form of fersie ‘hloride based on the total amount of the iron content in the aid solution In a further embodiment, bnshes 44 can be installed beeen the individual piling tanks as shown in FIG. 110 remove any loose scale adhering to the stip surface. As a result the pickling time ean generally be further reduced by 5-104 inal tests Brushes with abrasive particles, such as silicon carbide or sluminum oxide in tei bristles, are proven tobe a particu- lar advantage. The brushes can be positioned above and below the stainless stel strip to remove scale from both surfaces ofthe strip. ‘The following examples demonstrate preferred embodi- ments of the iavention, but are not intended to limit the scope ofthe invention EXAMPLE 1 Pickling ests were condicted on a stainless steel sp of| ‘grade AISI 409 in a pickling pilot plant comprising three Pickling tanks, each being 20 m long substantially as shown in FIG. 1. The operating conditions for the plant were as follows: “pickling tank 216 g HICT in total, 85 dissolved itoa, 84 g of which were Fe""and approx. 1 g Fe", 9 g Ce 2"pickting tank 200 g HCL in total, 60 g dissolved inoo, ail in the form of Fe", and approx. 7 g Ce“/L 3>piekling tank 195 g HCI in total, 35 g dissolved iron, 33 i of which were Fe, 2.@ Fe", 4 Cri ‘The temperature in all pickling tanks was 80° C. 42° C ‘The pickling acids were pumped into the pickling tanks at « rate of 150 mir from the ereulaion tanks assigned tothe respective circulation tank through the outlets ‘The first stainless ste! strip was transported through the piekling tanks ata rate of 30 m/min to provide a pickling in 0 3s 6 time of 120 sees. Minimal pickling was observed after the process. The same sirip was pulled throwgh the pickling fanks a socond time and then only approximately 50% de-scaling was observed. The sirip was not entirely free from scale until it was transported through the pickling tank ne mone time ata speed of 15 m/min. The overall pickling time was thus approximately 480 sec EXAMPLE 2 A pickling plant having three pickling tanks as in Example 1 was used inthis example, The chlorine gas was supplied to the cirevation tanks aod pickling tanks. ‘The ‘composition of the resulting acl solution in each tank was as follows: 1" pickling tank 216 g HCI in total, 85 g dissolved iron, $4 g of which were Fe™and approx. 31g Fel, 9g Crt 2, pickling tank 200 g HCI in total, 60 dissolved iron, 38 of which were Fe°, 22g Fe, 4 g CP*iL 3”>pickling tank 195 g HCY in total, 35 g dissolved itoa, 22 got which were Fe", 13 g Fe", 4g Ce“ ‘The temperature in all picking tanks was 80° C. +2° ‘Ata reduced speed of 15 m/min, the stainless steel sip had tobe conveyed through te pickling tanks twiee in order to obiain a suriace completely ftee from scale. The overall Pickling time was thus unchanged at 480 secs, EXAMPLE 3 ‘The fei eblorde conceateation i the pickling tanks was further increased by adding hydrogen peroxide othe suction Pipes leading othe eentctugal pump for pumping the acid solution through the circulation tank. The composition ofthe cid solution were adjusted as follows: 1" picking tank 216 HCH in total, 85.g dissolved iron, 38 g of which were Fe*and approx. 473 Fe", 34 Fe™, 9g CP*/12™ pickling tank 200 g ICL in fot, 60 g disslved iron, 26g of which were Fe", 34 Fe, 7g Ce*/l 3" pickling tank 195 g HCL in fofal 35 g dissolved iron, 15 g of which were Fe=*20 3 Fes 4g. "The temperature in all pickling tanks was 80° C. +2° . ‘The strip was fre from scale after passing through the pickling tanks only once ata speed of 15mimin. The overall Pieking time inthis est was ony 240 sees EXAMPLE 4 ‘The acid solution of Example 3 was adjusted to oxidize substantially all of the soluble iron to Fe™by addition of ‘oxidants in each of the tanks, The stainless slcel strip was ‘earied through the pickling baths at 80°C. The pickling lime of the stainless steel strip was unchanged from Example 3, ‘The table of FIG. 2 shows the results of Examples It with the pickling times expressed asa fraction based on the Pickling time of Example 1. The pickling time of Example Twas used as a base line for comparing with the pickling time of Examples 2-4 EXAMPLES 5-8 ‘The concentration ofthe pickling tanks of Examples 5-8. were adjusted as in Examples 1-4, respectively. The lem- peratures of the pickling acid was adjusted to 90° C, The pickling times are shown in the table of FIG. 3 and are ‘expressed a8 a faction based on the pickling time of Example 5. By increasing the temperature to 90° C,, the ‘peed could be increased to 18m/min atthe concentrations ‘of Examples 14 with satisfactory pickling, The picklingUS 6,250,314 BL 7 tanks of Example 7 have the concentrations as in Example 3 provided a pickling time of 200 secon EXAMPLES 9-14 “The pickling tanks of Examples 9-14 having intial icon and acid conceatrations as in Examples 1-4, respectively were adjusted with perchloric acid to increase the Ferrie chloride concentration. The amount of perchloric acid added ine acid solution was ealeulated as & percentage based oo the theoretical prchiorie acid consumption according to the ‘equation ‘The pickling times of Examples 10-14 are shown in the lable of FIG. 4 as a fraction of the pickling for the acid solution of Example 9, without the addition of perchlorie acid. Thus, Example 9 with 0% pereblorie acid serves as the base line for calculating the reduction i pickling times. With the successive addition of 10% by volume perchloric sci, the pickling ime was also reduced successively, These ‘examples show tat at least 50% of the dissolved metals being present in the form of ferric chloride provides improved pickling performance and reduced pickling times. EXAMPLES 15-18 ‘The pickling tanks of Examples 15-18 were adjusted to the iron and acid concentrations as io Examples 1-4. A. stainless steel strip of AISI 430 was transported through the acid solution according to the procedure of Examples 1-4 ‘The comparative pickling times are shown in the table of FIG. § using the pickling time of Example 13s a base line for calculating the improvemeats in pickling times. for Examples 15-18, EXAMPLES 19-22 “The pickling tanks of Examples 19-22 were adjusted to the iron and acid concentrations as in Examples 1-4. A. ‘stainless see! strip of AISI 304 was transported through the tanks according to the procedures of Examples 1-4. The ‘comparative pickling times are shown in th table of FIG. 6 using the pickling time of Example 1 as a base fine for caleulating the improvements in pickling time for Examples 19.22. Various embodiments have been chosen to illustrate the {nvention, It wil be apparent to those skilled in the art that rious modification can be made t0 the process without departing from the invention as defined in the appended claims. ‘What is claimed: 1. A process for pickling stainless steel comprising the steps of Feeding 4 stainless stel article ito a pickling tank eon- Taining aqueous hydrochloric acid solution, and pick- ling said stainless steel article to form Fe*"as fetrous chloride (FeCl) and Fes ferric ebloride(FeCI,) in said hydrochloric acid solution, and continuously adding an oxidant to said hydrochloric acid solution in an amouot in proportion to a surface arca of the slainless steel artic to oxidize said Fe™"10 Foto ‘mainlain a least about one third of a total dissolved iron conteat as ferric chloride in said hydrochloric acid solution, said oxidant being selected from the group consisting of nitric acid, chlorine, hydrogen peroxide, chlorine-oxygen compounds, and ferrie chloride 2. The process of claim 1, wherein in 3s 8 said aqueous hyrochloric acid solution is at tempera ture below the boiling point of an azcotropic hye chlorie acid solution 3. The process of claim 1, wherein said chromium-onygen ‘compound is 4 chromate 4. The process of claim 1, wherein said ehlorine-oxygen ‘compound is a chlorine containing acid '. The process of claim 1, comprising adding ssid oxidant in an amount to maintain at least, shout one half of suid total dissolved iron content in said hydrochloric acid solution a ferric chloride. 6. The process of claim 1, comprising the step of meas suring a content of said ferri¢ chloride of suid hydrochloric acid solution by measuring the density, conductivity, or ‘oxidation reduction potential, by photometric analysis of ‘tid hydrochloric acid solution or a combination thereof 7. The process of claim 1, comprising determining the surface area of said stainless steel article being pickled by Said hydolorie acid solution and adding said oxidant in an ‘amount based on Said surface area. 8, The process of claim 1, comprising determining the ‘weight of sad stainless steel article being pickled by said hydrochloric acid solution and adding said oxidant to said hydrochloric acid solution in an amount based on said ‘weight ‘9. The process of claim 1, wherein said pickling tank includes a circulating pump to ciculate said hydrochloric acid solution from an outlet pipe of sai tank to an inlet pipe ‘of said tank, and said method comprises adding said oxidant to said outlet pipe, 10. The process of claim 1, wherein said pickling tank including a circulating tank and si process comprises supplying said oxidant! to said pump {o feed said oxidant directly into said hydrochloric ac solution LL. The process of claim 1, comprising pumping said hhydrochlorie acid solution from said pickling tank to ‘circulation tank and adding said oxidant to said eieutation tank to oxidize Fe*to Fe. 12. The process of claim 1, comprising feeding said slainless steel article through a plurality of said acid pickling tanks arranged adjacent each other and mechanically clean= ing « surface of su article between adjacent pickling tanks. 13. The process of claim 6, comprising adding said ‘oxidant 10 said hydrochloric acid solution based on suid measured ferric chloride content to provide a fetie chloride ‘content of sai atleast one third based on said total dissolved iron content in said hydrochloric acid solution. 14. The process of claim 12, comprising brushing said surface of Said article between adjacent pickling tanks 10 remove seale from said surface. 18. Aprocessof pickling stainless stel strip comprising: providing a plurality of adjacent tanks arranged in series, each said tank containing an aqueous hydrochloric aid solution, eeding @ continuous stainless stel strip through said aqueous hydrochloric acid solutions in each of said piciling tanks to pickle the surface if said strip thereby Torming Fe**as ferrous chloride (FeCl) and Fe*as Terie chloride (FeCI,) in ssid aqueous hyrochloric acid solution, ae continuously supplying an oxidant to said aqueous hydro cblorie seid solution in each of said pickling tanks in an amount to oxidize atleast a portion of Fe™to Fe°*and to maintain a feric chloride content of at least about ‘one third based on a total soluble iron content in eachUS 6,250,314 BL 9 of said aqueous fydrochloric acd solutions in a pick- ling tanks, wherein said oxidant is selected from the {group consisting of nitric acid, chlorine, hydrogen peroxide, chlorine-oxygen compounkls, and ferric ehlo- Fide 16. The process of claim 15, wherein said aqueous hyde: Cclorie acid solution in each of said pickling tanks is maintained ata temperature of at least about 40° C, 17. The process of claim 18, wherein said oxidant is a ‘chromate 18. The process of claim 15, wherein said oxidant is @ chlorine containing acid. 19. The process of claim 15, wherein said oxidant is included in an amount to maintain said Tertic chloride content of atleast about one half based fon said total soluble icon content in said aqueous hylrochloric acid solution, 20, The process of claim 15, comprising the step of measuring the ferric chloride conteat in said aqueous bydo- ‘chloric acd solution by measuring the density, conductivity, ‘or oxidation reduction potential by photomeitic analysis of ‘tid aqueous hydrochloric acid Solution or combination thereof, and adding said oxidant to said aqueous bydeocto- ie acid solution based on said measured fertie chloride ‘content, 21. The process of claim 18, comprising determining a ‘weight of sad stainless steel article being pickled by said 10 aqueous hydrochloric ac solution and adding said oxidant in an amount based on said surface area 22. The process of claim 18, comprising determining a weight of stid stainless stel article being pickled by said 5 aqueous hydrochloric acid solution and adding said oxidant to said aqueous hydrochloric acid solution in an amount based on said weight, 23. The process of elaim 18, wherein Sid cid pickling tanks include a circulating pump 10 circulate said aqueous bydrochleri [tom an outlet pipe of said pickling tank to an inlet pipe of said pickling tank, and said method comprising adding said oxidant to said outlet pipe. 24, The process of elaim 18, wherein each of sid aqueous hydrochloric acid solution from an outlet pipe to an inlet pipe of said pickling tank, and said method comprises ‘supplying said oxidaot to said oxidant to said pump 10 feed ‘sid oxidant directly into said aqueous hydroeblorie acid 2 solution, 25. The process of claim 16, wherein said oxidant is included in an amount to maintain sad Terie chloride content of atleast about one half base ‘on said total soluble iron content in said aqueous hydrochloric acid solution, in