TR201603891A2 - PURE IRON POWDER PRODUCTION FROM DECAPAGE SOLUTIONS - Google Patents
PURE IRON POWDER PRODUCTION FROM DECAPAGE SOLUTIONS Download PDFInfo
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- TR201603891A2 TR201603891A2 TR2016/03891A TR201603891A TR201603891A2 TR 201603891 A2 TR201603891 A2 TR 201603891A2 TR 2016/03891 A TR2016/03891 A TR 2016/03891A TR 201603891 A TR201603891 A TR 201603891A TR 201603891 A2 TR201603891 A2 TR 201603891A2
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- compounds
- iron
- reduction
- fexoy
- thermal decomposition
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 95
- 230000008569 process Effects 0.000 claims abstract description 82
- 239000002253 acid Substances 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 26
- 238000005554 pickling Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 18
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 230000009467 reduction Effects 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 229910005084 FexOy Inorganic materials 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000011946 reduction process Methods 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 150000002506 iron compounds Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 238000001465 metallisation Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 6
- 238000004381 surface treatment Methods 0.000 abstract description 5
- 230000007928 solubilization Effects 0.000 abstract 1
- 238000005063 solubilization Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical class Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000012256 powdered iron Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- 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
- C23G1/36—Regeneration of waste pickling liquors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
Mevcut buluş demir içerikli materyaller, ve bilhassa çelik malzemelere ve yassı çelik ürünlere uygulanan yüzey işlemleri veya demir esaslı malzemelerin çözümlendirilmesi sonucunda oluşan asit çözeltilerinden yüksek metalizasyon oranına sahip saf elementel demirin elde edilmesine yönelik bir proses ile ilgilidir. Buluşun tercih edilen yapılanmalarında söz konusu proses, ayrıca dekapaj prosesinden çıkan atık asit çözeltisinden asidin geri kazanılmasını da ihtiva etmektedir.The present invention relates to a process for obtaining pure elemental iron with high metallization ratio from acid solutions resulting from surface treatments applied to ferrous materials, in particular steel materials and flat steel products, or solubilization of iron-based materials. In preferred embodiments of the invention, the said process also includes the recovery of acid from the waste acid solution from the pickling process.
Description
Tarifname DEKAPA] ÇÖZELTILERINDEN SAF DEMIR TOZU ÜRETIMI Bulusun Ilgili Oldugu Teknik Alan Mevcut bulus genel olarak demir içerikli malzemelerin, yüzey islemleri sirasinda uygulanan asidik dekapaj islemi sonunda olusan asidik çözeltilerden saf demir tozu üretimi yöntemi ile ilgilidir. Mevcut bulus özellikle dekapaj islemi sonunda olusan asidik çözeltilerden demir bilesiklerinin geri kazanilarak özel bir proses dahilinde islenmesi ve saf demirin yüksek metalizasyon orani ile elde edilmesine yönelik bir yöntem ile ilgilidir. specification PRODUCTION OF PURE IRON POWDER FROM DEKAPA] SOLUTIONS Technical Field of the Invention The present invention is generally used for surface treatment of ferrous materials. Pure iron powder from the acidic solutions formed at the end of the applied acidic pickling process. related to the production method. The present invention is particularly useful for acidic acidic products formed at the end of the pickling process. Recovering iron compounds from solutions and processing them in a special process and relates to a method for obtaining pure iron with a high metallization rate.
Teknigin Bilinen Durumu Otomotiv, beyaz esya, elektrik direkleri, bariyerler vb. alanlarda kullanilan yassi çelik ürünler uzun ömürlü olmalari adina genellikle galvanizleme olarak tanimlanan farkli metallerle (çinko, nikel, krom, vb.) kaplama islemi öncesi asidik bir yüzey temizleme islemine tabi tutulmaktadirlar. Bunun disinda çelik ve demir esasli sac levhalar, civatalar, somunlar ve teller gibi farkli amaçli ürünlerin de kaplanmasi yaygin olarak kullanilan bir uygulamadir. State of the Art Automotive, white goods, power poles, barriers etc. flat steel used in fields In order to ensure longevity of the products, different types of products, generally defined as galvanizing an acidic surface cleaning before plating with metals (zinc, nickel, chrome, etc.) they are subject to the order. Apart from this, steel and iron-based sheet plates, bolts, Coating of multi-purpose products such as nuts and wires is a widely used method. is the application.
Kaplama yapilacak çelik malzemeler üzerinde önceki proseslerden kaynaklanan yag, kir veya pas bulunmasi durumunda basarili bir kaplama islemi gerçeklestirilememektedir. Oil, dirt caused by previous processes on the steel materials to be coated In the presence of rust or rust, a successful coating process cannot be performed.
Ayrica galvanizleme öncesinde kaplamanin veya boyanin çelik malzemeye iyi tutunmasini saglamak için de dekapaj islemi uygulanmaktadir. Bu nedenle tüm kaplama proseslerinde oldugu gibi galvanizleme öncesinde de söz konusu çelik malzemeler ön yüzey hazirlama islemlerine tabi tutulmaktadirlar. In addition, before galvanizing, it is necessary to ensure that the coating or paint adheres well to the steel material. The pickling process is applied to ensure Therefore, in all coating processes As well as before galvanization, the steel materials in question should be prepared for the preliminary surface preparation. they are subject to scrutiny.
Asidik yüzey temizleme asamasi olarak bilinen “Dekapaj” özellikle çeligin yüzeyinde olusan oksit tabakasinin bir asit banyosunda (HCl, HzSO4] çözündürülüp temizlenerek, üretilen çelige daha temiz ve standart bir yüzey kazandirmak için yapilan bir islemdir. Pickling, known as the acidic surface cleaning stage, is especially on the surface of the steel. by dissolving and cleaning the formed oxide layer in an acid bath (HCl, HzSO4), It is a process done to give the produced steel a cleaner and standard surface.
Geçmiste demir çelik sektöründe dekapaj amaciyla sülfürik asit banyolari yaygin olarak kullanilirken, 1960'lardan itibaren daha kaliteli ve daha homojen yüzeylere sahip ürün kalitesinin elde edilmesi için hidroklorik asit (HCl) içerikli banyolar yayginlasmaya baslamistir. Hidroklorik asit [HCD daha hizli sonuç alinmasi, düsük asit tüketimi ve pirometalurjik rejenerasyonun daha kolay ve daha ekonomik olmasindan dolayi özellikle tercih edilen bir asit banyosudur. Dekapaj isleminde, 1 ton çelik için yaklasik 0.30 kg HCl kullanilmaktadir. Çelik saclarin yüzey temizligi için uygulanan dekapaj islemi sonrasinda olusan çürük asit de denilen atik çözelti, demirce zengin bir çözeltidir. Söz konusu çözelti, bunun yaninda serbest hidroklorik asit, çelik bilesiminde bulunan ve HCl içinde çözünebilen metal iyonlarinin yani sira hatali ürün geri dönüsü gerçeklestirilmis ise bir miktar da çinko iyonu da içerebilmektedir. In the past, sulfuric acid baths were widely used for pickling in the iron and steel industry. products with higher quality and more homogeneous surfaces since the 1960s. Baths containing hydrochloric acid (HCl) are becoming widespread in order to obtain the quality of has started. Hydrochloric acid [HCD gives faster results, lower acid consumption and Especially since pyrometallurgical regeneration is easier and more economical. is a preferred acid bath. In the pickling process, approximately 0.30 kg of HCl per 1 ton of steel is used. The rotten acid formed after the pickling process applied for the surface cleaning of steel sheets The waste solution, also called waste solution, is an iron-rich solution. The solution in question is free hydrochloric acid, metal found in the steel composition and soluble in HCl In addition to the ions, if the wrong product is returned, some zinc may contain ions.
Dekapaj islemlerinde kullanilan asit banyosuna ve demirin yüzeyinde olusmus oksit yapisina bagli olarak gerçeklesen reaksiyonlar farklilik göstermektedir. Hidroklorik asit çok genis araliklarda degiskenlik göstermekte olup, bu çözeltilerin geri kazanimi için uygulanacak yöntemin belirlenmesi oldukça zordur. Kullanilmis asidik yüzey temizleme çözeltilerinin geri kazanim yöntemleri kazanim amaci bakimindan iki grupta toplanmaktadir. Ilki asit geri dönüsümü ikincisi ise asit içerisinde olusan metalin geri dönüsümüdür. Asit geri dönüsümü veya rejenerasyonu için kullanilan yöntemler elektrodiyaliz, difüzyon diyalizi, membran distilasyonu, buharlastirma veya sprey kavurma yöntemleridir. Metalin geri kazanimi için ise solvent ekstraksiyon, retardasyon, iyon degistirme ve kristalizasyon gibi yöntemler kullanilmaktadir. The oxide formed on the surface of the iron and the acid bath used in the pickling processes Depending on its structure, the reactions that take place differ. Hydrochloric acid It varies in very wide ranges and is used for the recovery of these solutions. It is very difficult to determine the method to be applied. Used acidic surface cleaning The recovery methods of the solutions are divided into two groups in terms of recovery purpose. is being collected. The first is acid recycling and the second is the recycling of the metal formed in the acid. is the transformation. Methods used for acid recycling or regeneration electrodialysis, diffusion dialysis, membrane distillation, evaporation or spray roasting methods. For metal recovery, solvent extraction, retardation, methods such as ion exchange and crystallization are used.
Dekapaj asit çözeltilerinden asit ve ayni zamanda demir bilesiklerinin geri kazanimi, ekonomik deger arz ettigi için 1900'lerin basindan beri ilgi odagi olmustur. Örnegin GB 190300423-A sayili belgede sülfürik asit veya hidroklorik asit ile yürütülen bir dekapaj proses banyosunda asit ve demir oksidin geri kazanilmasi için ortama toprak alkali karbonat bilesiklerinin ilave edilmesi ön görülmüstür. Recovery of acid as well as iron compounds from pickling acid solutions, It has been the focus of attention since the early 1900s because of its economic value. eg GB In document 190300423-A, a pickling carried out with sulfuric acid or hydrochloric acid alkaline earth to the medium to recover acid and iron oxide in the process bath The addition of carbonate compounds is envisaged.
FeSO4 içeren bir dekapaj çözeltisinden demir bilesiklerinin geri kazanilmasina yönelik bir deneme GB 656,003 no'lu patent dokümaninda açiklanmistir. Burada kullanilan proses, sodyum amalgam gibi bir indirgeyici ajan ile suyun demir vitriol ile bir araya getirilmesi, ve en nihayetinde demirin çöktürülerek geri kazanilmasini içermektedir. Fakat bu proses HCl asit banyosu kullanilan dekapaj prosesleri için bir çözüm getirmedigi gibi civali bir indirgeyici ajan kullanmasi itibari ile günümüzde çevresel nedenlerle uygulanmasi, maliyetli ve saglik açisindan tehlikelidir. varan ve daha tercihen 860-1200°C araliginda olmasi istenen yüksek sicakliklara isitilarak hidrojen ile muamele edilmesi suretiyle indirgenmesi, ve akabinde sinterlenmesi islemini açiklamaktadir. Ancak saf demir eldesinde sinterlesme büyük bir sorundur ve özellikle akiskan yatak gibi dinamik sistemlerde akis yollari kolayca tikanmaktadir. Ayrica sinterlesen ürün tercih sebebi degildir ve ögütülmesi gerekir. A method for the recovery of iron compounds from a pickling solution containing FeSO4. The trial is described in the patent document GB 656,003. The process used here is combining water with iron vitriol with a reducing agent such as sodium amalgam, and ultimately the recovery of iron by precipitation. But this process HCl does not provide a solution for pickling processes using acid bath, as well as a mercury solution. Today, it is applied for environmental reasons due to the use of reducing agents, It is costly and dangerous to health. to high temperatures, up to and more preferably in the range of 860-1200°C. reduction by heating with hydrogen, followed by explains the sintering process. However, sintering is a major factor in obtaining pure iron. is a problem and especially in dynamic systems such as fluidized beds, the flow paths are easily is clogged. In addition, the sintered product is not preferred and must be grinded.
Diger yandan demir oksit bilesiklerinin hidrojen ile indirgenmesinde yüksek metalizasyon oraninin yakalanmasi önemli bir sorundur. Elementel demirin ekonomik deger arz etmesi için yüksek saflikta (>%99] olmasi gerekir. Indirgenme reaksiyonlarinin kinetigi, indirgeyici maddenin difüzyonuna bagimli oldugundan sabit yatakli reaktörler veya diger konvansiyonel ekipmanlarla reaksiyon gerçeklestirildiginde yüksek oranda saf demirin elde edilmesi zor veya imkansiz olmakta, ya da uzun süreli muameleyi gerektirmektedir. Mevcut bulus kapsaminda birinci kademede uygulanan akiskan yatakta dekompozisyon islemi ile dekapaj islemi sonunda olusan çürük asit bilesiminde bulunan asidin geri dönüsümü saglanirken, çürük asit içerisinde olusan demir içerikli bilesiklerden [FeClz ve az miktarda FeClg) saf demiroksit (Fex0y] ve bozunma ürünü olarak da HCl elde edilmektedir. Yöntem kapsaminda gerçeklestirilen ikinci islem adimi saf demiroksit (Fex0y] bilesiklerinin akiskan yatakli bir sistemde hidrojen ve/veya CO benzeri bir redüktan gaz ile redüksiyonu esasina dayanmaktadir. Bu islemde gerçeklesen reaksiyonlarin son ürünlerinin saf demir (Fe) ve su buhari olmasindan dolayi çevresel atik yükü olusturmadan yüksek metalizasyon oranlarina (>%99) sahip saf demir tozu üretimi mümkün olmaktadir. Birinci islem adiminda olusan saf demiroksit [Fex0y) partikül boyutu islem sicakligi, asi malzeme miktari, retardasyon süresi gibi parametreler ile kontrol edilebilirken ayni zamanda elde edilen saf demiroksit (FexOy) taneciklerinin kolay ögütülebiliyor olmasindan faydalanarak da istenilen boyuta indirgenmesi mümkündür. Bulusun amaci yukarida belirtilen önceki teknige ait problemleri ve kisitlamalari minimize ederek dekapaj çözeltilerinden asit ve saf demirin istenilen nitelikte, kisa sürede, düsük maliyetle elde edilmesidir. Bu amaçlara, istem 1'e göre açiklanan bir yöntem ile ulasilmaktadir. On the other hand, the reduction of iron oxide compounds with hydrogen Capturing the metallization rate is an important problem. Economics of elemental iron It must be of high purity (>99%] to be of value. Fixed bed reactors as their kinetics are dependent on the diffusion of the reducing agent. highly pure when reacted with or with other conventional equipment iron is difficult or impossible to obtain, or prolonged treatment requires. Within the scope of the present invention, the fluidized bed applied in the first stage found in the rotten acid composition formed at the end of the decomposition process and the pickling process. While the recycling of the acid is ensured, the iron-containing acid formed in the rotten acid pure iron oxide (Fex0y) and its degradation product from the compounds [FeClz and a small amount of FeClg] HCl is also obtained. The second process step performed within the scope of the method pure iron oxide (Fex0y] compounds in a fluidized bed system with hydrogen and/or CO It is based on reduction with a similar reducing gas. If you happen in this name environmental effects due to the fact that the end products of the reactions are pure iron (Fe) and water vapour. Pure iron powder with high metallization rates (>99%) without generating waste load production is possible. Pure iron oxide [Fex0y] formed in the first processing step Parameters such as particle size, processing temperature, amount of graft material, retardation time While it can be controlled with the pure iron oxide (FexOy) particles obtained at the same time, It can be reduced to the desired size by taking advantage of its easy grinding. possible. The object of the invention is the above-mentioned prior art problems and By minimizing the restrictions, acid and pure iron from the pickling solutions quality, in a short time, at low cost. For these purposes, according to claim 1 achieved by the method described.
Bulusun Kisa Açiklamasi Mevcut bulus, demir içerikli bir malzemenin, özellikle de yassi çeligin yüzey islemine tabi tutuldugu bir dekapaj prosesine ait asidik çözeltiden saf demir elde etmek üzere bir proses sunmaktadir. Proses, temel olarak asagidaki adimlari ihtiva etmektedir: - demir içerikli malzemenin bir asit çözeltisi ile (yüzeyde mevcut oksit tabakasinin giderilmesi veya farkli bir isleme hazirlamak üzere veya sadece bu prosese uygun bir çözelti elde etmek amaciyla) muamele edilmesi - asitle çözümlendirme (yüzey temizleme) isleminin ardindan söz konusu çözeltide mevcut demir klorür bilesiklerine termal dekompozisyon isleminin uygulanmasi, - termal dekompozisyon islemi sirasinda ortama demir oksit ilavesi ile asilama yapilmasi ve katmanli yapida FexOy bilesiklerinin elde edilmesi, - olusan katmanli yapida FexOy bilesiklerinin bir akiskan, sabit veya döner yatak içerisinde bir redüktan madde ile temas haline getirilmesi ve demir bilesiklerinin indirgenmesi, ve - indirgeme sonunda saf demir tozunun geri oksidasyonuna izin vermeden sogutulmasi ve ticari saflikta demir tozunun elde edilmesi. Brief Description of the Invention The present invention relates to the surface treatment of a ferrous material, particularly flat steel. to obtain pure iron from the acidic solution of a pickling process in which provides the process. The process basically includes the following steps: - with an acid solution of the ferrous material (the oxide present on the surface in order to remove the layer of water or to prepare it for a different process or just for this to obtain a solution suitable for the process) - after acid leaching (surface cleaning) thermal decomposition to ferric chloride compounds present in solution. implementation, - grafting with the addition of iron oxide during the thermal decomposition process making and obtaining FexOy compounds in a layered structure, - a fluid, fixed or rotary bed of FexOy compounds in a layered structure formed in contact with a reducing agent and reduction of compounds, and - without allowing back-oxidation of pure iron powder at the end of reduction cooling and obtaining commercial grade iron powder.
Bulus konusu proseste kullanilan asit tercihen hidroklorik asittir (HCl). Burada bahsi geçen termal dekompozisyon islemi tercihen bir akiskan yatak içerisinde ve 500°C ila 1000°C arasinda bir sicaklikta gerçeklestirilebilmektedir. The acid used in the process of the invention is preferably hydrochloric acid (HCl). bet here The thermal decomposition process is preferably in a fluidized bed and at 500°C to It can be carried out at a temperature of 1000°C.
Prosesin FeXOy bilesiklerini indirgeme asamasinda redüktan olarak tercihen Hz veya CO, daha tercihen Hz kullanilmaktadir. Ayrica bu asamada olusan suyun sistemden tahliyesi tercih edilen bir husustur. Söz konusu indirgeme islemi yukarida belirtildigi gibi 500°C'nin üzerinde bir sicaklikta gerçeklesebilmektedir. Ancak sinterlesmenin olumsuz etkilerinin minimize edilmesi için 600-800°C, daha tercihen yaklasik 650°C olan bir sicaklik degerinde indirgeme isleminin verimli bir sekilde yürütülebildigi görülmüstür. Preferably Hz or CO as a reducer in the process to reduce FeXOy compounds, more preferably Hz is used. In addition, the discharge of water formed at this stage from the system is a preferred issue. The reduction process in question is as stated above. It can take place at a temperature above 500°C. However, the sintering a temperature of 600-800°C, more preferably about 650°C, to minimize the effects of It has been observed that the reduction process in the temperature value can be carried out efficiently.
Yine burada kullanilan redüktan bir Hz/Nz gaz karisimini ihtiva edebilir ki burada Hz/Nz hacimsel orani 1:1'den büyük, daha tercihen 2:1 veya bundan büyük olabilir. Again, the reducer used here may contain a Hz/Nz gas mixture, where Hz/Nz the volumetric ratio may be greater than 1:1, more preferably 2:1 or greater.
Termal dekompozisyon isleminde FexOy bilesiklerinin olusmasi sirasinda asilama yaparak katmanli yapida FexOy taneciklerinin elde edilmesi avantajli bulunmustur. En nihayetinde elde edilen elementel demir de bu sayede katmanli yapida olusmaktadir. Inoculation during the formation of FexOy compounds in the thermal decomposition process It has been found advantageous to obtain FexOy particles in a layered structure by Most Finally, the elemental iron obtained is formed in a layered structure by this means.
Bahsi geçen FeXOy bilesiklerinin redüksiyona tabi tutulan tanecikleri tercihen 300 ila 1000 um, daha tercihen 300 ila 600 um araliginda partikül boyutuna sahiptir. Bu sayede ögütme gibi materyal kalitesine olumsuz etkisi olan ilave islemler elimine edilmektedir. The reduced particles of said FeXOy compounds preferably range from 300 to 1000 It has a particle size in the range of µm, more preferably 300 to 600 µm. In this way Additional processes such as grinding, which have a negative impact on material quality, are eliminated.
Sekillerin Kisa Açiklamasi Sekil 1, mevcut bulusa göre sunulan prosesin termal dekompozisyon safhasinda asilama yapilarak elde edilen FexOy taneciklerinin SEM görüntüsüdür. Brief Description of Figures Figure 1, grafting in the thermal decomposition phase of the process presented according to the present invention is the SEM image of the FexOy particles obtained by
Sekil 2, ortam sicakligi ve hidrojen kismi basincina bagli faz kararlilik diyagramini göstermektedir. Figure 2 shows the phase stability diagram depending on ambient temperature and hydrogen partial pressure. shows.
Sekil 3, sicaklik ve Hz/Nz oranina bagli olarak % metalizasyonu gösteren diyagramdir. Figure 3 is the diagram showing % metallization based on temperature and Hz/Nz ratio.
Sekil 4a, 500°C sicaklikta Hz/Nz hacimsel oraninin 2:1 oldugu bir denemede 60 dk. boyunca yürütülen redüksiyon islemi sonucunda elde edilen demir taneciklerinin SEM görüntüsünü sunmaktadir. Figure 4a, 60 min. in an experiment with a 2:1 Hz/Nz volumetric ratio at 500°C. SEM of the iron particles obtained as a result of the reduction process carried out throughout presents the image.
Sekil 4b, 1000°C sicaklikta Hz/Nz hacimsel oraninin 2:1 oldugu bir denemede 60 dk. boyunca yürütülen redüksiyon islemi sonucunda elde edilen demir taneciklerinin SEM görüntüsünü sunmaktadir. Figure 4b, 60 min. in an experiment with a Hz/Nz volumetric ratio of 2:1 at 1000°C. SEM of the iron particles obtained as a result of the reduction process carried out throughout presents the image.
Bulusun Ayrintili Açiklamasi Mevcut bulus kapsaminda, demir içerikli materyallere, özellikle de çelik malzemelere yüzey islemleri sirasinda uygulanan asidik (HCl) dekapaj islemi sonunda olusan atik asidik çözeltilerden saf demir tozu üretimine yönelik bir proses açiklanmaktadir. Söz konusu proses istege bagli olarak ayrica proseste kullanilan çürük asidin rejenerasyonu ve geri kazanimini ihtiva etmektedir. Detailed Description of the Invention Within the scope of the present invention, ferrous materials, especially steel materials Waste generated at the end of acidic (HCl) pickling process applied during surface treatments A process for producing pure iron powder from acidic solutions is described. Promise The subject process is optionally also regeneration of rotten acid used in the process. and its recovery.
Bahsi geçen yöntem kapsaminda öncelikli olarak metal malzemelere uygulanan asidik temizleme sonucunda olusan atik asit çözeltisine Termal Dekompozisyon islemi uygulanmakta ve bu islem sonunda demir oksit bilesikleri [FexOy] elde edilmektedir. Daha sonra elde edilen FexOy bilesiklerine akiskan yatakta bir redüktan (indirgeyici) ile redüksiyon uygulamasi gerçeklestirilerek katma degeri yüksek saf demir tozu elde edilmektedir. Within the scope of the aforementioned method, acidic materials applied primarily to metal materials Thermal Decomposition process to the waste acid solution formed as a result of cleaning is applied and at the end of this process, iron oxide compounds [FexOy] are obtained. More FexOy compounds obtained after Pure iron powder with high added value is obtained by performing the reduction application. is being done.
Prosesin ilk asamasini teskil eden metal malzemelere uygulanan dekapaj islemi sirasinda olusan bazi reaksiyonlar asagidaki sekildedir: FeO + ZHCI -> FeClz + HzO 6FeCl3 + 3Fe -› 9FeClz Söz konusu dekapaj isleminin neticesinde muamele edilen çelik veya demir içerikli malzeme yüzeyinde bulunan oksitler temizlenmekte ve ileri asamada yüzey islemlerine hazir hale gelmektedir. Proses banyosunda ise genel olarak kullanilmis HCl, demir iyonlari, çinko iyonlari ve demir klorür bilesikleri bulunmaktadir. Çözelti bilesiminde çelik yapisindan gelen ve asitte çözünen metalklorürler de mevcuttur. During the pickling process applied to metal materials constituting the first stage of the process Some of the reactions that occur are as follows: FeO + ZHCI -> FeClz + HzO 6FeCl3 + 3Fe -› 9FeClz Steel or iron containing treated as a result of the said pickling process The oxides on the surface of the material are cleaned and in the advanced stage, surface treatments are required. is getting ready. In the process bath, generally used HCl, iron ions, zinc ions and ferric chloride compounds. In solution composition There are also acid-soluble metal chlorides from the steel structure.
Mevcut bulus kapsaminda gerçeklestirilen dekapaj isleminde tercihen 60-200 g/l Fe2+ iyonu ve 25-100g/l konsantrasyonlarinda serbest HC] asidi bulunmaktadir. Dekapaj islemi sonrasinda genel olarak FeClz (ve kismen FeCl3] formunda demir klorür bilesikleri elde edilmektedir. In the pickling process carried out within the scope of the present invention, preferably 60-200 g/l Fe2+ ion and free HC] acid at 25-100g/l concentrations. pickling After processing, ferric chloride compounds are generally in the form of FeClz (and partially FeCl3]. is obtained.
Bulusa göre sunulan prosesin ikinci asamasinda elde edilen demir klorür ve HCl içerikli dekapaj çözeltisi Termal Dekompozisyon islemine tabi tutularak demir oksit bilesiklerinin elde edilmesi amaçlanmaktadir. Bu uygulama sirasinda gerçeklesen reaksiyonlardan bazilari asagida verilmektedir: Termal dekompozisyon islemi sirasinda HCl ve demir klorür bilesiklerini içeren kirli asit çözeltisi dekompozisyona ugrayarak HCl ve ara ürün olarak da FexOy bilesikleri elde edilmektedir. Bulusun tercih edilen yapilanmalarinda bu islem bir akiskan yatak içerisinde gerçeklestirilerek dekompozisyon reaksiyonlarinin hizlandirilmasi ve HCl gazinin tahliyesinin kolaylastirilmasi mümkün olmaktadir. Islem sirasinda tercihen 750°C ila 950°C, daha tercihen 850°C ila 900°C arasinda bir sicaklik kullanimiyla reaksiyonlarin ideal olarak gerçeklestirilebilecegi görülmüstür. Ferric chloride and HCl content obtained in the second stage of the process presented according to the invention. The pickling solution is subjected to the Thermal Decomposition process and iron oxide compounds are intended to be obtained. occurred during this application. Some of the reactions are given below: Dirty acid containing HCl and ferric chloride compounds during the thermal decomposition process Its solution decomposes to obtain HCl and FexOy compounds as intermediates. is being done. In preferred embodiments of the invention, this process is a fluidized bed. Accelerating the decomposition reactions by performing in HCl It is possible to facilitate the evacuation of gas. Preferably 750°C during processing The reactions take place using a temperature of between 850°C and 900°C, more preferably between 850°C and 900°C. It has been seen that it can be realized ideally.
Bulus, bir baska yönü ile, saf demir elde etmenin yaninda termal dekompozisyon sonucu ortaya çikan gaz halde HCl'nin dekapaj banyosunda yeniden kullanilmak üzere geri kazanimini saglayan ilave bir proses islemini ihtiva edebilmektedir. Buna göre rejenere edilen gaz haldeki asit konvansiyonel yöntemlerle termal dekompozisyon reaksiyonlarinin gerçeklestirildigi ortamdan çekilerek sogutulup depolanabilmekte veya dekapaj islemine geri beslenebilmektedir. Termal dekompozisyon isleminin akiskan yatak içerisinde gerçeklestirilmesi durumunda gaz haldeki rejenere asidin daha kolay ve verimli sekilde geri kazanilacagi görülmüstür. Rejenere asit, örnegin bir fan yardimi ile bir siklon içerisine çekilerek demir oksit taneciklerinden ayristirilabilir. Akabinde asit buhari ventüriye gelir ve sicakligi yaklasik 100°C'ye kadar düsürülebilir. Örnegin absorplayicilara alinabilen rejenere asit, üzerine su püskürtülerek kullanima hazir asidik çözelti olusturulabilir. In another aspect, the invention can be obtained by obtaining pure iron as well as by thermal decomposition. The resulting gaseous HCl is recycled to be reused in the pickling bath. It may include an additional process process that provides the recovery. Accordingly, regenerated Thermal decomposition of gaseous acid by conventional methods It can be cooled and stored by withdrawing from the environment where the reactions take place or can be fed back into the pickling process. Fluid of thermal decomposition process gaseous regenerated acid is easier and It has been seen that it can be recovered efficiently. Regenerated acid, for example with the aid of a fan It can be separated from the iron oxide particles by being drawn into a cyclone. Then the acid steam enters the venturi and its temperature can be reduced to approximately 100°C. For example regenerated acid, which can be taken into absorbers, is ready to use by spraying water on it. solution can be created.
Bulusa göre sunulan prosesin üçüncü asamasinda, termal dekompozisyon sirasinda elde edilen FexOy bilesiklerinin bir redüktan kullanilarak indirgeme islemi yapilmakta ve elementel halde saf demir elde edilmektedir. Bu islemin yapilmasinda birçok sorun görüldügünden önceki teknikte yer alan ticari yöntemlerde [sabit yatakli sistemlerde redüksiyon) demir oksit bilesiklerinin elde edilmesinin ötesine gidilememis ve su ana kadar verimli bir proses ile ticarilesme saglanamamistir. Mevcut bulus kapsaminda bu problemleri asmak Için yürütülen çalismalarda FexOy bilesiklerinin bir redüktan ile gerçeklesen reaksiyonlarinin kinetik olarak difüzyon engelli oldugu fark edilmistir. Ayrica indirgenme reaksiyonlari sicaklik ve redükleyici/tasiyici gaz oranindan büyük ölçüde etkilenmektedir. Yapilan denemelerde sicaklik 1100°C'ye çikarilip redükleyici (H2)/tasiyici (Nz) gaz orani 1:1 oldugunda bile metalizasyon oraninin %21-22 seviyelerinde kaldigi görülmüstür. Ayrica sinterlesme büyük bir sorundur ve redüksiyon asamasinda olusan FeO film tabakasi sinterlesmede önemli rol oynamaktadir. In the third step of the process presented according to the invention, it is obtained during thermal decomposition. The reduction process of the obtained FexOy compounds is carried out using a reducer and elemental pure iron is obtained. Many problems in doing this operation prior art commercial methods [in fixed bed systems] reduction) could not go beyond obtaining iron oxide compounds and the main Commercialization could not be achieved with such an efficient process. In the context of the present invention, this In the studies carried out to overcome the problems, FexOy compounds were combined with a reducer. It was noticed that the reactions that took place were kinetically diffusion-impaired. Moreover reduction reactions are greatly affected by temperature and reducing/carrier gas ratio. is affected. In the experiments, the temperature was increased to 1100°C and the reducer was Even when the (H2)/carrier (Nz) gas ratio is 1:1, the metallization ratio is 21-22%. levels were observed. Also sintering is a big problem and reduction The FeO film layer formed during the sintering stage plays an important role in sintering.
Bulus sahipleri, yukarida bahsedilen difüzyon kisitlamasinin, redüksiyon asamasinda akiskan yatak kullanilmasi durumunda ortadan kaldirildigini bulmuslardir. Demir oksit taneciklerinin redüktan gazla temas yüzeyi arttigindan verimde ciddi bir artis gözlemlenmistir. Fakat faydali etkisi olmasina ragmen akiskan yatakta istenen metalizasyon oraninin yakalanamadigi ve sinterlesmenin hala önemli bir sorun oldugu gözlemlenmistir. Bulus sahipleri bu problemleri asmak üzere, yukarida anlatilan termal dekompozisyon basamaginda bir asilama islemi gerçeklestirerek Sekil 1'de gösterilen katmanli yapida demir oksit bilesiklerini elde etmislerdir. Asilama islemi dekompozisyon reaksiyon ortamina demir oksit asilama malzemesi ilave edilmesi ile yapilabilmektedir. The inventors are aware of the above-mentioned diffusion restriction at the reduction stage. They found that it is eliminated if a fluidized bed is used. iron oxide As the contact surface of the particles with the reducing gas increases, there is a serious increase in efficiency. has not been observed. However, although it has a beneficial effect, the desired metallization rate cannot be achieved and sintering is still an important problem. has not been observed. In order to overcome these problems, the inventors use the above-described thermal by performing a grafting process in the decomposition step, as shown in Figure 1. They obtained iron oxide compounds in a layered structure. Grazing process decomposition It can be done by adding iron oxide grafting material to the reaction medium.
Bu tabakali yapinin bilhassa difüzyon bariyeri problemini beklenmedik sekilde ortadan kaldirdigi, FeXOy bilesiklerinin redüksiyon kinetigini iyilestirdigi ve yüksek oranda metalizasyon (>%99 Fe) elde edilebilmesinde önemli rol oynadigi görülmüstür. This layered structure unexpectedly eliminates the diffusion barrier problem in particular. removed, FeXOy compounds improved the reduction kinetics and it was highly It has been seen that it plays an important role in obtaining metallization (>99% Fe).
Buna göre Termal dekompozisyon islemi sonunda asilama ile olusturulan demiroksit (FeXOy) bilesikleri akiskan yatakta bir redüktan ile temas haline getirilmekte ve en nihayetinde saf toz demir (Fe) elde edilmektedir. Bahsi geçen redüktan, tercihen Hz veya CO, daha tercihen Hz gazidir. Fakat CH4 gibi teknigin bilinen durumunda mevcut baskaca indirgeyici gazlar da kullanilabilir. Redüktan olarak Hz kullanilmasi durumunda F exOy kati bilesiklerinin akiskan yatakta redüksiyonu temel olarak üç asamada gerçeklestirilmektedir. Söz konusu reaksiyon asamalari asagida verilmektedir: 6Fe0 + 6H2 -› 6Fe + 6H20 Dolayisiyla toplam reaksiyon: FexOy + yHz -› XFe + yH20 seklindedir. Accordingly, the iron oxide formed by grafting at the end of the thermal decomposition process (FeXOy) compounds are brought into contact with a reducer in a fluidized bed and Finally, pure powdered iron (Fe) is obtained. Said reducer, preferably Hz or The CO is more preferably Hz gas. However, in the state of the art, such as CH4, there are other Reducing gases can also be used. In case of using Hz as a reducer, F exOy solid The reduction of the compounds in the fluidized bed basically takes place in three stages. is carried out. The mentioned reaction steps are given below: 6Fe0 + 6H2 -› 6Fe + 6H20 So the total reaction is: It is in the form of FexOy + yHz -› XFe + yH20.
Sekil 2'de ortam sicakligi ve hidrojen kismi basincina bagli faz kararlilik diyagrami gösterilmektedir. Ortam hidrojen kismi basincini düsürmek ve reaksiyon hizini arttirmak amaciyla reaksiyon ürünü su buharinin sistemden uzaklastirilmasi mümkündür. Phase stability diagram depending on ambient temperature and hydrogen partial pressure in Figure 2 is shown. To lower the ambient hydrogen fraction pressure and increase the reaction rate For this purpose, it is possible to remove the reaction product water vapor from the system.
Susuzlandirma adi verilen islem sayesinde reaksiyon sonucu olusan su sistemden uzaklastirilmaktadir. Saf hidrojen ile gerçeklestirilen reaksiyonda tek gaz ürünün su buhari olmasi ve kondensasyon ile uzaklastirilabilmesi prosesi hizlandirmaktadir. Suyu uzaklastirilan gaz tekrar sisteme beslenerek reaksiyonlarin devam etmesi saglanabilmektedir. Yukarida açiklanan redüksiyon prosesinin 600°C ve üzeri bir sicaklikta yürütülmesi durumunda 0/o Metalizasyon oraninda ciddi bir artis fark edilmistir. Thanks to the process called dewatering, the water formed as a result of the reaction is removed from the system. being removed. In the reaction with pure hydrogen, the only gas product is water. The fact that it has steam and can be removed by condensation accelerates the process. juice The gas that is removed is fed back to the system and the reactions continue. can be provided. At a temperature of 600°C and above, the reduction process described above A serious increase in the metallization rate of 0/o has been noticed when it is carried out at a temperature of 0/o.
Ayrica hidrojen/azot karisimi bir redüktan gaz sisteminin redüksiyon ortamina beslendigi durumda Hz/Nz hacimsel oraninin 1:1'den büyük, daha tercihen yaklasik 2:1 ve üzeri olmasi durumunda % metalizasyon oraninda yine artis gözlemlenmektedir. Bu etkiler Sekil 3'te verilen deneme sonuçlarindan açikça görülebilmektedir. Bu nedenle en iyi etkilerin görüldügü redüksiyon kosullarinda sicakligin 650-1000°C araliginda olmasi, ve Hz/Nz indirgeyici sisteminin kullanilmasi durumunda Hz/Nz hacimsel oraninin 1:1'den büyük olmasi tercih edilmektedir. Ayrica FeXOy bilesiklerinin redüksiyona tabi tutulan taneciklerinin boyutu 300 ila 600 nm arasinda tutuldugunda sinterlesmenin beklenmedik sekilde minimize edildigi ve indirgeyici difüzyonunun reaksiyon kinetiginde bir limitasyon arz etmedigi fark edilmistir. In addition, hydrogen/nitrogen mixture can be added to the reduction medium of a reducing gas system. where the Hz/Nz volumetric ratio is greater than 1:1, more preferably about 2:1 and above, an increase is observed in the % metallization rate. This effects can be clearly seen from the trial results given in Figure 3. Therefore the most in the reduction conditions where good effects are seen, the temperature is between 650-1000°C, and the Hz/Nz volumetric ratio is greater than 1:1 if the Hz/Nz reducing system is used. Larger is preferred. In addition, the reduction of FeXOy compounds sintering is unexpected when the size of the particles is kept between 300 and 600 nm. It is minimized in such a way and the reductive diffusion has an effect on the reaction kinetics. It has been noticed that there is no limitation.
Sekil 4a, 500°C sicaklikta Hz/Nz hacimsel oraninin 2:1 oldugu bir denemede 60 dk. boyunca yürütülen redüksiyon islemi sonucunda elde edilen demir taneciklerinin SEM görüntüsünü sunmaktadir. Bu denemede %46 metalizasyon degerine ulasilmistir. Figure 4a, 60 min. in an experiment with a 2:1 Hz/Nz volumetric ratio at 500°C. SEM of the iron particles obtained as a result of the reduction process carried out throughout presents the image. Metallization value of 46% was reached in this experiment.
Sekil 4b ise 1000°C sicaklikta Hz/Nz hacimsel oraninin 2:1 oldugu bir denemede 60 dk. boyunca yürütülen redüksiyon islemi sonucunda elde edilen demir taneciklerinin SEM görüntüsünü sunmaktadir. Bu denemede %99.98 metalizasyon degerine ulasilmistir. Figure 4b, on the other hand, is 60 minutes in an experiment where the Hz/Nz volumetric ratio is 2:1 at 1000°C. SEM of the iron particles obtained as a result of the reduction process carried out throughout presents the image. In this experiment, 99.98% metallization value was reached.
Her iki deneme de göstermektedir ki metalizasyon orani üzerinde sicakligin önemli bir rolü vardir. Ayrica Sekil 4a ile 4b beraber dikkate alindiginda redüksiyonun beklendigi üzere distan içe dogru ve topokimyasal olarak ilerledigi açikça görülmüstür. Asit rejenerasyon sisteminde (termal dekompozisyon asamasinda) asilama malzemesi üzerinde tabakali olarak olusan FeXOy yapisi nedeni ile redüklenmis yapida da ayni olusum gözlenmistir. Bu tabakali yapi, redüksiyon esnasinda gaz geçisini ve reaksiyon ürünü su buharinin çikisini kolaylastirdigindan dolayi deneysel çalismalarda redüksiyonu engelleyen veya zorlastiran bir difüzyon bariyeri olusumu gözlenmemistir. Bu yapinin etkisi ile redüksiyon süresinin 60 dakikanin altinda tutulmasi mümkün olmaktadir. Saf hidrojen kullanilmasi durumunda proses süresinin daha da azalmasi mümkündür. Both trials show that temperature has a significant effect on the metallization rate. has a role. In addition, when Figures 4a and 4b are considered together, it is expected that reduction It was clearly seen that it progressed from the outside to the inside and topochemically. Acid grafting material in the regeneration system (in the thermal decomposition stage) It is the same in the reduced structure due to the FeXOy structure formed as a layer on it. formation is observed. This layered structure prevents gas passage and reaction during reduction. Since the product facilitates the exit of water vapor, its reduction in experimental studies No diffusion barrier formation was observed that hinders or complicates it. Do this With its effect, it is possible to keep the reduction time under 60 minutes. Pure In the case of using hydrogen, it is possible to further reduce the process time.
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| TR2016/03891A TR201603891A2 (en) | 2016-03-25 | 2016-03-25 | PURE IRON POWDER PRODUCTION FROM DECAPAGE SOLUTIONS |
| EP17162167.5A EP3231537B1 (en) | 2016-03-25 | 2017-03-21 | Production of elemental iron powder from pickling solutions |
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| CA844536A (en) * | 1970-06-16 | Kudryk Val | Recovery of sulfur and iron oxide from pyritic materials | |
| GB190300423A (en) | 1903-01-07 | 1903-12-10 | Henry William Hemingway | Improvements in the Treatment of Waste Pickle Liquor for the Removal or Utilisation of Free Acid Contained therein. |
| GB662051A (en) * | 1948-01-06 | 1951-11-28 | Davide Primavesi | Improved chemical process for producing powdered iron |
| GB656003A (en) | 1948-03-18 | 1951-08-08 | Erzhutte Ag | A process for the simultaneous recovery of base metals in powder form and of metallic salts |
| SE306096B (en) * | 1965-06-23 | 1968-11-18 | Centro Speriment Metallurg | |
| GB1219674A (en) | 1968-10-07 | 1971-01-20 | British Iron Steel Research | Process for the production of iron powder from aman oxide |
| US4414021A (en) * | 1982-05-06 | 1983-11-08 | Welbon William W | Process for the synthesis of iron powder |
| JPS59145707A (en) * | 1983-02-10 | 1984-08-21 | Furukawa Mining Co Ltd | Production of ferromagnetic metallic powder |
| AT399516B (en) * | 1993-07-21 | 1995-05-26 | Andritz Patentverwaltung | METHOD FOR REGENERATING Hydrochloric Acid From Pickling Plants |
| US6962685B2 (en) * | 2002-04-17 | 2005-11-08 | International Business Machines Corporation | Synthesis of magnetite nanoparticles and the process of forming Fe-based nanomaterials |
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