RS53411B

RS53411B - METHOD OF REMOVING METALS FROM AQUATIC MEDIUM CONTAINING METALS

Info

Publication number: RS53411B
Application number: RS20060392A
Authority: RS
Inventors: Branislav Petrusevski; Saroj Kumar Sharma; Jan Cornelis Schippers
Original assignee: Ihe Delft
Priority date: 2003-12-23
Filing date: 2003-12-23
Publication date: 2014-10-31

Abstract

Postupak za uklanjanje metala iz vode koja sadrži metale, u kome se pomenuta voda dovodi u dodir sa materijalom-nosačem, gde materijal-nosač funkcioniše kao adsorpcioni medijum za metale, pri čemu postupak obuhvata sledeće stepene (faze):a) obezbeđivanje filtracionog medijuma već obloženog hidroksidom gvožda kao materijala-nosača,b) dovođenje u dodir materijala-nosača dobijenog u stepenu a) sa vodom tako da se dobije odvodna voda,c) prekidanje stepena b) kada sadržaj metala u odvodnoj vodi prede određenu vrednost,d) regenerisanje (obnavljanje) materijala-nosača iz stepena c), i po mogućstvue) ponavljanje stepena b)-d),naznačen time, što se pomenuti stepen d) regeneracije (obnavljanja) izvodidovođenjem u dodir pomenutog materijala-nosača sa rastvorom Fe(II). Prijava sadrži još 9 patentnih zahteva.A process for removing metals from water containing metals, wherein said water is contacted with a carrier material, wherein the carrier material functions as an adsorption medium for metals, the process comprising the following steps (a): a) providing a filtration medium already coated with iron hydroxide as carrier material, b) contacting the carrier material obtained in step a) with water to obtain drainage water, c) interrupting step b) when the metal content in the drainage water exceeds a certain value, d) regeneration ( the restoration of the carrier material from step c), and preferably the repetition of steps b) to d), wherein said step d) is regenerated by contacting said carrier material with Fe (II) solution. The application contains 9 more patent claims.

Description

Ovaj pronalazak se odnosi na postupak za uklanjanje metala iz vode koja sadrži metale, u kome se pomenuta voda dovodi u dodir sa materijalom-nosačem, pri čemu materijal-nosač funkcioniše kao adsorpcioni medijum za metale. This invention relates to a process for removing metals from water containing metals, in which said water is brought into contact with a carrier material, wherein the carrier material functions as an adsorption medium for the metals.

Takav postupak je poznat iz međunarodne prijave WO 94/06717, gde se voda koja sadrži metale propušta kroz čestični materijal-nosač u prisustvu rastvora Fe (II) i oksidanta, takvom brzinom i u takvom pravcu da se materijal-nosač u vodi fluidizuje. Kada takvi Fe (II) joni dođu u dodir sa površinom materijala-nosača u prisustvu oksidanta, Fe (II) joni se adsorbuju na površini materijala-nosača, a adsorbovani Fe (II) joni se zatim oksidišu čime se formiraju Fe (III) joni koji se zatim brzo prevode u hidroksid gvožđa putem reakcije sa vodom. Sloj tako formiranog hidroksida gvožđain situse ponaša kao adsorbent za metale ili može da reaguje sa metalima koji se nalaze u vodi, pri čemu se metali tada vezuju za čestice materijala-nosača. Na osnovu eksperimentalnih rezultata koji su prikazani u Tabeli 5 napred pomenute međunarodne prijave, na primer, efikasnost uklanjanja npr. arsena je početno niska, naime iznosi 65.3%, nakon čega se ta efikasnost lagano povećava do vrednosti od približno 99.8%. Na osnovu ovih merenja očigledno je da odvodna voda iz reaktora sadrži značajnu količinu metala na početku postupka, što je čini neprikladnom za ljudsku upotrebu. Prilikom odlivanja odvodne vode u površinsku vodu, visoki sadržaj gvožđa takođe može predstavljati problem. Iako efikasnost uklanjanja, posle izvesnog vremena, dostiže vrednost od više od 99%, odvodna voda koja je dobijena na početku postupka je još uvek jako zagađena teškim metalima. Jedan nedostatak takvog postupka je činjenica da je često teško u praksi odrediti trenutak u kome se postiže visok stepen efikasnosti, posebno u onim slučajevima gde se ne koristi skupocena oprema za analize. S obzirom da materijal-nosač mora biti u fluidizovanom stanju, moraju se ispuniti posebni zahtevi u vezi sa dimenzijama materijala-nosača. To znači da je samo frakcija sa tačno određenom veličinom čestica pogodna za primenu za takav postupak. Such a procedure is known from the international application WO 94/06717, where water containing metals is passed through a particulate carrier material in the presence of a solution of Fe (II) and an oxidant, at such a speed and in such a direction that the carrier material in the water is fluidized. When such Fe (II) ions come into contact with the surface of the carrier material in the presence of an oxidant, the Fe (II) ions are adsorbed on the surface of the carrier material, and the adsorbed Fe (II) ions are then oxidized to form Fe (III) ions which are then rapidly converted to iron hydroxide by reaction with water. The iron hydroxide layer thus formed in situ acts as an adsorbent for metals or can react with the metals in the water, whereby the metals then bind to the particles of the carrier material. Based on the experimental results shown in Table 5 of the aforementioned international application, for example, the removal efficiency of e.g. arsenic is initially low, namely 65.3%, after which the efficiency increases slightly to a value of approximately 99.8%. Based on these measurements, it is obvious that the reactor effluent contains a significant amount of metals at the beginning of the process, which makes it unsuitable for human consumption. When draining sewage into surface water, high iron content can also be a problem. Although the removal efficiency, after some time, reaches a value of more than 99%, the drainage water obtained at the beginning of the process is still heavily polluted with heavy metals. One disadvantage of such a procedure is the fact that it is often difficult in practice to determine the moment when a high degree of efficiency is achieved, especially in those cases where expensive analytical equipment is not used. Since the carrier material must be in a fluidized state, special requirements regarding the dimensions of the carrier material must be met. This means that only the fraction with a precisely determined particle size is suitable for use in such a procedure.

Dokument Jens Moller: „uklanjanje rastvorenih teških metala iz nakupljene površinske kišnice pomoću peska obloženog gvožđe oksidom" iznet na međunarodnoj konferenciji o komunalnim otpadnim vodama 8. septembra 2002. god, str. 1-11 opisuje postupak za odstranjivanje rastvorenih teških metala u površinskom toku kišnice korišćenjem peska obloženog gvožđe oksidom čija se regeneracija vrši potapanjem u blagi kiseli rastvor. Paper by Jens Moller: "removal of dissolved heavy metals from accumulated surface rainwater using iron oxide coated sand" presented at the International Municipal Wastewater Conference on September 8, 2002, p. 1-11 describes a process for removing dissolved heavy metals in surface runoff using iron oxide-coated sand that is regenerated by immersion in a mild acid solution.

Dokument US 5,075,010 opisuje postupak uklanjanja gvožđa i mangana iz podzemnih voda korišćenjem sloja čestica od granula antracita, kvarcnog peska ili plastičnih granula sa kontinualnim obrazovanjem i regeneracijom obloge od gvožđe hidrokisda korišćenjem Fe<2+>koje je već prisutno u vodi u kombinaciji sa aeracijom i kontrolisanjem Fe<3+>i pH vrednosti vode po aeraciji. Document US 5,075,010 describes a process for removing iron and manganese from groundwater using a layer of particles made of anthracite granules, quartz sand or plastic granules with continuous formation and regeneration of an iron hydroxide coating using Fe<2+> already present in the water in combination with aeration and controlling the Fe<3+> and pH value of the water after aeration.

U dokumentu Sharma S: Adsorpciono uklanjanje gvožđa iz podzemnih voda (Adsorptive iron removal from ground water) iz decembra 2001. god. opisan je postupak koji je fokusiran samo na uklanjanje gvožđa, dok se predmetni pronalazak odnosi na uklanjanje više metala (uključujući arsen, olovo, hrom, bakar, kadmijum, nikl i selen). Za razliku od postupka opisanog u navedenom dokumentu predmetni pronalazak predviđa: (a) novu kombinaciju faza koja za rezultat ima brojne prednosti tehnologije uklanjanja metala i (b) novu kompenzacionu fazu regeneracije koja je za razliku od poznatih pristupa intermitentna, kratka i bazirana na visokoj koncentraciji Fe(II) koje se dozira samo u toku ove faze. In the document Sharma S: Adsorption iron removal from ground water (Adsorptive iron removal from ground water) from December 2001. a process is described that focuses only on iron removal, while the present invention relates to the removal of multiple metals (including arsenic, lead, chromium, copper, cadmium, nickel and selenium). In contrast to the procedure described in the mentioned document, the present invention foresees: (a) a new combination of phases which results in numerous advantages of metal removal technology and (b) a new compensation phase of regeneration which, unlike known approaches, is intermittent, short and based on a high concentration of Fe(II) which is dosed only during this phase.

Cilj ovog pronalaska je da se obezbedi postupak za uklanjanje metala iz vode koja sadrži metale, pri čemu se visoka efikasnost uklanjanja teških metala postiže već od samog početka. The aim of the present invention is to provide a process for the removal of metals from water containing metals, whereby a high efficiency of heavy metal removal is achieved right from the start.

Sledeći cilj ovog pronalaska je da se obezbedi postupak za uklanjanje metala iz vode koja sadrži metale, pri čemu do sada važeći kritični zahtevi u vezi sa određenom veličinom čestica materijala-nosača više nemaju značaja. A further object of the present invention is to provide a process for the removal of metals from water containing metals, whereby the hitherto valid critical requirements regarding a certain particle size of the carrier material are no longer relevant.

Sledeći cilj ovog pronalaska je da se obezbedi postupak za uklanjanje metala iz vode koja sadrži metale, pri čemu se materijal-nosač, koji je zasićen metalima, može obnoviti na jednostavan i efikasan način. A further object of the present invention is to provide a process for the removal of metals from water containing metals, wherein the carrier material, which is saturated with metals, can be regenerated in a simple and efficient manner.

Sledeći cilj ovog pronalaska je da se obezbedi postupak za uklanjanje metala iz vode koja sadrži metale, kojim će se koristi materijal-nosač koji je dostupan u velikim količinama.. A further object of the present invention is to provide a process for the removal of metals from metal-containing water using a carrier material that is available in large quantities.

Pronalazak, kao što je opisan u uvodu, naznačen je time što postupak sadrži sledeće stepene: a) obezbeđivanje filtracionog medijuma koji je obložen hidroksidom gvožđa i koji će imati ulogu materijala-nosača, b) dovođenje u dodir materijala-nosača koji je dobijen u stepenu a) sa vodom tako da se dobije odvodna voda, c) završetak stepena b) kada sadržaj metala u odvodnoj vodi pređe određenu vrednost, d) obnavljanje materijala-nosača iz stepena c) dovođenjem u dodir pomenutog The invention, as described in the introduction, is characterized by the fact that the process contains the following stages: a) providing a filtration medium that is coated with iron hydroxide and which will act as a carrier material, b) bringing the carrier material obtained in stage a) into contact with water so that drainage water is obtained, c) ending stage b) when the metal content in the drainage water exceeds a certain value, d) recovering the carrier material from stage c) by bringing it into contact with said

materijala-nosača sa rastvorom Fe (II), i po mogućstvu carrier material with Fe (II) solution, and preferably

e) ponavljanje stepena b)-d). e) repetition of steps b)-d).

Jedan ili više ciljeva ovog pronalaska postižu se izvođenjem ovde opisanog postupka. One or more objects of the present invention are achieved by carrying out the process described herein.

Potrebno je posebno naglasiti daje ovde opisani pronalazak efikasan neposredno po početku stepena b). Odvodna voda koja je dobijena u stepenu b) smatra se vodenim tokom, a sadržaj metala u njoj je niži od sadržaja metala u vodi iz koje se metali uklanjanju. Primenom specijalnog materijala-nosača, posebno filtracionog medijuma obloženog hidroksidom gvožđa, dobija se tok odvodne vode koji ne sadrži teške metale i to neposredno pošto je voda dovedena u dodir sa materijalom-nosačem. Primenom opisanog postupka efikasnost uklanjanja je veća od 99% već na samom početku. S obzirom na to, da se visok stepen efikasnosti postiže od trenutka kada su voda i materijal-nosač dovedeni u međusobni kontakt, tako dobijena odvodna voda je pogodna za upotrebu, na primer kao voda za piće pogodna za ljudsku upotrebu. It should be emphasized that the invention described here is effective immediately after the beginning of step b). The drainage water obtained in step b) is considered a water flow, and the metal content in it is lower than the metal content in the water from which the metals are removed. By using a special carrier material, especially a filtration medium coated with iron hydroxide, a flow of drainage water that does not contain heavy metals is obtained immediately after the water is brought into contact with the carrier material. By applying the described procedure, the removal efficiency is greater than 99% already at the very beginning. Considering that a high degree of efficiency is achieved from the moment when the water and the carrier material are brought into mutual contact, the resulting drainage water is suitable for use, for example as drinking water suitable for human consumption.

Uobičajeni uslovi postupka su: The usual conditions of the procedure are:

prečnik materijala-nosača = 0.8-5.0 mm, diameter of the carrier material = 0.8-5.0 mm,

brzina filtracije = 0.5-20-0 m/h, poželjno 5.0-10.0 m/h, filtration speed = 0.5-20-0 m/h, preferably 5.0-10.0 m/h,

trajanje stepena a-b) = u prošeku nekoliko nedelja, duration of degrees a-b) = several weeks on average,

ukupna dubina filtracionog sloja = 0.5-4.0 m, poželjno 2.0-3.0 m. total depth of the filtration layer = 0.5-4.0 m, preferably 2.0-3.0 m.

Podrazumeva se daje filtracioni medijum uređen kao nepokretni sloj, ali u posebnim varijantama poželjno je rasporediti određen broj pojedinačnih filtracionih jedinica, posebno 2-3 filtracione jedinice, u seriji, pri čemu se svaka filtraciona jedinica može obnoviti posebno, a da pri tom nije potrebno isključiti celokupnu instalaciju. Pored toga, moguće je da svaka filtraciona jedinica u seriji funkcioniše po proizvoljnom redosledu. It goes without saying that the filtration medium is arranged as a stationary layer, but in special variants it is desirable to arrange a certain number of individual filtration units, especially 2-3 filtration units, in series, whereby each filtration unit can be renewed separately, without the need to turn off the entire installation. In addition, it is possible for each filtration unit in series to operate in an arbitrary order.

S obzirom na to, da će materijal-nosač posle izvesnog vremena biti zasićen metalima koji se uklanjanju iz vodene sredine, sadržaj metala u odvodnoj vodi će biti viši od unapred određene vrednosti. Drugim rečima, unapred određena granična vrednost sadržaja metala u odvodnoj vodi je prekoračena. To znači da materijal-nosač koji je zasićen metalom mora biti podvrgnut postupku regeneracije (obnavljanja), pri čemu se taj postupak posebno izvodi spajanjem materijala-nosača iz stepena c) sa rastvorom Fe (II). Fe (II) se adsorbuje na površini materijala-nosača u toku stepena d) u kome se vrši regeneracija, a Fe (II) se takođe i oksiduje kao rezultat prisustva kiseonika u vodenoj sredini. Takođe je moguće koristiti oksidaciona sredstva, kao što su ozon, vodonik-peroksid, kalijumpermanganat, hlor i slično. Kao rezultat toga, na materijalu-nosaču je formirana nova površina, pri čemu takva površina može da funkcioniše kao novo adsorpciono mesto za teške metale koji se uklanjaju. Given that, after some time, the carrier material will be saturated with metals that are removed from the water environment, the metal content in the drainage water will be higher than the predetermined value. In other words, the predetermined limit value of the metal content in the drainage water was exceeded. This means that the carrier material that is saturated with metal must be subjected to a regeneration (renewal) procedure, whereby this procedure is specifically performed by combining the carrier material from step c) with the Fe (II) solution. Fe (II) is adsorbed on the surface of the carrier material during step d) in which regeneration is carried out, and Fe (II) is also oxidized as a result of the presence of oxygen in the water environment. It is also possible to use oxidizing agents, such as ozone, hydrogen peroxide, potassium permanganate, chlorine and the like. As a result, a new surface is formed on the support material, where such surface can function as a new adsorption site for the heavy metals to be removed.

Takav se postupak regeneracije može se ponoviti nekoliko puta. Jedna prednost takvog postupka regeneracije je činjenica da se materijal-nosač obnavlja brzo i efikasno, pri čemu nisu potrebne velike količine hemikalija. Osim toga, rastvor Fe (II) je dostupan na veliko i po niskoj ceni kao sporedni proizvod industrije obrade čelika. U prethodno razmatranoj međunarodnoj prijavi WO 94/06717, u toku stepena adsorpcije vrši se kontinuirano doziranje rastvora koji sadrži Fe (II), pri čemu se uvek meri sadržaj Fe (II) u odvodnoj vodi. Ovo znači da odvodna voda koja je dobijena iz postupka prema međunarodnoj prijavi WO 94/06717 uvek sadrži određenu količinu Fe (II), što negativno utiče na njenu dalju upotrebu, na primer kao vode za piće ili tehničke vode. Osim toga, prisustvo Fe (II) može imati negativan uticaj na mogućnost oticanja odvodne vode u površinsku vodu, posebno u slučaju obrade otpadne vode. Pored toga, postupak prema međunarodnoj prijavi WO 94/06717 zahteva kontinuirano doziranje rastvora Fe (II). Podrazumeva se da takvo kontinuirano doziranje ne samo da povećava troškove, već istovremeno predstavlja i dopunski teret za korisnika. Such a regeneration procedure can be repeated several times. One advantage of such a regeneration process is the fact that the carrier material is regenerated quickly and efficiently, without the need for large amounts of chemicals. In addition, Fe(II) solution is available in bulk and at low cost as a by-product of the steel processing industry. In the previously discussed international application WO 94/06717, during the adsorption step, a solution containing Fe (II) is continuously dosed, whereby the content of Fe (II) in the drain water is always measured. This means that the waste water obtained from the process according to the international application WO 94/06717 always contains a certain amount of Fe (II), which negatively affects its further use, for example as drinking water or technical water. In addition, the presence of Fe (II) can have a negative impact on the possibility of drainage water flowing into surface water, especially in the case of wastewater treatment. In addition, the process according to the international application WO 94/06717 requires continuous dosing of the Fe (II) solution. It goes without saying that such continuous dosing not only increases costs, but also represents an additional burden for the user.

Filtracioni medijum obložen oksidom gvožđa koji je korišćen u ovom pronalasku izabran je iz grupe koju čine pesak, kamen plavac, antracit ili njihova kombinacija, posebno je korišćen pesak iz postojećeg postrojenja za prečišćavanje podzemne vode. Takav tip peska dostupan je na veliko, a on već ima omotač od oksida gvožđa. The iron oxide coated filtration medium used in this invention is selected from the group consisting of sand, pumice stone, anthracite or a combination thereof, in particular sand from an existing ground water treatment plant was used. This type of sand is available in bulk, and it already has an iron oxide coating.

Specifični uslovi postupka za stepen regeneracije jesu: The specific conditions of the procedure for the degree of regeneration are:

brzina filtracije = 5-50 m/h, poželjno 10-20 m/h, filtration speed = 5-50 m/h, preferably 10-20 m/h,

sadržaj Fe (II) = 50-200 mg/l, content of Fe (II) = 50-200 mg/l,

trajanje = 0.5-2 časa, duration = 0.5-2 hours,

pH vrednost = 5.0-8.0, poželjno 6.0-7.0. pH value = 5.0-8.0, preferably 6.0-7.0.

Prethodno navedeni uslovi za regeneraciju mogu se takođe prilagoditi, ako je neophodno, na primer, sadržaj Fe (II) može biti povećan do vrednosti neposredno ispod granice rastvorljivosti Fe (II). Opisani postupak regeneracije može se posebno izvesti u jednom i istom kontejneru ili filtracionoj jedinici, što znači da se adsorpcioni stepeni a)-c), kao i stepen d) regeneracije izvode u istom kontejneru (sudu) ili filtracionoj jedinici. U praksi će ovo imati veliki značaj. U posebnoj varijanti takođe je moguće, sa druge strane, ukloniti materijal-nosač, koji je zasićen jonima metala, i obnoviti ga izvan kontejnera, na primer spajanjem sadržaja drugih adsorpcionih jedinica. The aforementioned regeneration conditions can also be adjusted, if necessary, for example, the Fe (II) content can be increased to a value just below the Fe (II) solubility limit. The described regeneration procedure can be carried out separately in one and the same container or filtration unit, which means that adsorption stages a)-c), as well as stage d) of regeneration are performed in the same container (vessel) or filtration unit. In practice, this will be of great importance. In a special variant, it is also possible, on the other hand, to remove the carrier material, which is saturated with metal ions, and restore it outside the container, for example by combining the contents of other adsorption units.

Postupak prema ovom pronalasku se može koristiti za istovremeno uklanjanje, između ostalog, sledećih teških metala: olova, arsena, hroma, žive, bakra, mangana, nikla, kadmijuma i selena, pri čemu su ovi metali prisutni u vodi u rastvorenom obliku. The process according to the present invention can be used for the simultaneous removal of, among others, the following heavy metals: lead, arsenic, chromium, mercury, copper, manganese, nickel, cadmium and selenium, where these metals are present in water in dissolved form.

Pogodna voda je na primer podzemna voda, voda za piće, tehnička voda, industrijska (otpadna) voda i površinska voda, pri čemu je predstavljeni pronalazak posebno pogodan za pripremu vode za piće kao i za preradu industrijske (otpadne) vode. S obzirom na to, da se regeneracija materijala-nosača iz stepena c) izvodi spajanjem materijala-nosača sa rastvorom koji sadrži Fe (II), poželjno je da se materijal-nosač ispere vodenim rastvorom, posebno vodom koja ima visok sadržaj kiseonika, pre ponovnog izvođenja adsorpcionih stepena a)-c), tako da se uklone pahuljice gvožđa, a kao rezultat toga oksidacija Fe (II) na površini materijala-nosača biće nastavljena. Takođe je moguće, u posebnoj varijanti, upotrebiti vodeni tok koji sadrži hemikalije, na primer ozon, hlor, vodonik-peroksid, kalijumpermanganat. Kada se koristi takav tretman, pahuljice gvožđa neće ulaziti u tokove odvodne vode koji su se formirali u toku postupka regeneracije. Suitable water is, for example, underground water, drinking water, technical water, industrial (waste) water and surface water, whereby the presented invention is particularly suitable for the preparation of drinking water as well as for the processing of industrial (waste) water. Given that the regeneration of the carrier material from step c) is performed by combining the carrier material with a solution containing Fe (II), it is preferable to wash the carrier material with an aqueous solution, especially water that has a high oxygen content, before re-performing the adsorption stages a)-c), so that the iron flakes are removed, and as a result, the oxidation of Fe (II) on the surface of the carrier material will continue. It is also possible, in a special variant, to use a water stream containing chemicals, for example ozone, chlorine, hydrogen peroxide, potassium permanganate. When such a treatment is used, iron flakes will not enter the wastewater streams formed during the regeneration process.

U predstavljenom postupku, stepen b) se izvodi na takav način da se materijal-nosač može smatrati nepokretnim slojem, što znači da fluidizacija nosača koja je bila potrebna prema međunarodnoj prijavi \VO 94/06717, više nije neophodna. In the presented procedure, stage b) is performed in such a way that the carrier material can be considered as a stationary layer, which means that fluidization of the carrier, which was required according to the international application \VO 94/06717, is no longer necessary.

Da bi se postigao intenzivan kontakt između vode koja sadrži metale i materijala-nosača, stepen b) se poželjno izvodi na takav način da se voda propušta u pravcu na gore kroz sloj materijala-nosača. Podrazumeva se, međutim, da ovaj postupak ne isključuje propuštanje vode u pravcu na dole kroz sloj materijala-nosača. In order to achieve an intensive contact between the metal-containing water and the carrier material, step b) is preferably carried out in such a way that the water is passed in an upward direction through the layer of the carrier material. It should be understood, however, that this procedure does not preclude water permeation in a downward direction through the layer of carrier material.

Da bi se postigao manji pad pritiska kroz nepokretni sloj materijala-nosača, poželjno je da materijal-nosač prema stepenu a) ima prosečan prečnik od 0.8-5.0 mm. In order to achieve a lower pressure drop through the stationary layer of carrier material, it is preferable that the carrier material according to step a) has an average diameter of 0.8-5.0 mm.

Ovaj će pronalazak će sada biti detaljnije objašnjen kroz određen broj primera, sa pozivom na priložene dijagrame. This invention will now be explained in more detail through a certain number of examples, with reference to the attached diagrams.

Slika 1 je šematski prikaz efikasnosti uklanjanja mangana iz vodenog toka. Figure 1 is a schematic representation of the efficiency of manganese removal from a water stream.

Slika 2 je šematski prikaz uklanjanja arsena iz vodene kompozicije. Figure 2 is a schematic representation of the removal of arsenic from an aqueous composition.

Slika 3 je šematski prikaz regeneracije filtracione jedinice posle određenog broja stepena regeneracije. Figure 3 is a schematic representation of the regeneration of the filtration unit after a certain number of stages of regeneration.

Slika 4 je šematski prikaz uticaja ciklusa obavljanja na uklanjanje arsena iz vodene kompozicije. Figure 4 is a schematic representation of the effect of the performance cycle on the removal of arsenic from the aqueous composition.

Slika 5 je šematski prikaz uklanjanja teških metala iz vode. Figure 5 is a schematic representation of the removal of heavy metals from water.

U nastavku se navode primeri izvođenja pronalaska. Svi primeri su izvedeni na način koji je dat u prethodnom opisu i sa parametrima datim u prethodnom opisu, koji se ovde neće ponovo navoditi. The following are examples of embodiments of the invention. All examples were performed in the manner given in the previous description and with the parameters given in the previous description, which will not be repeated here.

Primer 1 Example 1

Podzemna voda koja sadrži mangan, arsen i gvožđe u količinama od 3.13 mg/l, 417 u.g/1 i 3.45 mg/l, redom, propuštana je kroz filtracionu jedinicu koja sadrži filtracioni medijum obložen hidroksidom gvožđa kao materijal-nosač, primenom prosečne brzine filtracije od 0.2 m/h i prosečnog vremena kontakta od 58 minuta. Rezultati ovog eksperimenta su grafički prikazani na Slici 1, na kojoj se vidi daje efikasnost uklanjanja u toku određenog vremenskog perioda znatno iznad 90%. Groundwater containing manganese, arsenic, and iron in amounts of 3.13 mg/l, 417 u.g/1, and 3.45 mg/l, respectively, was passed through a filtration unit containing iron hydroxide-coated filtration media as a carrier material, using an average filtration rate of 0.2 m/h and an average contact time of 58 minutes. The results of this experiment are shown graphically in Figure 1, which shows that the removal efficiency over a certain period of time is well above 90%.

Primer 2 Example 2

U ovom je primeru model kompozicije podzemne vode propuštan kroz filtracionu jedinicu, pri čemu filtraciona jedinica sadrži pesak obložen hidroksidom gvožđa. Dubina filtracionog sloja je bila 2.4 m i brzina filtracije 2 m/h. Kompozicija podzemne vode koja je imala funkciju tečnog modela imala je sledeći sadržaj arsena (V) = 250 ± 50 u.g/1, P04 " = 0.25 ± 0.10 mg kao P i HC03" = 250 ± 20 mg/l, sa pH vrednošću 7.7. Rezultat je grafički prikazan na slici 2, sa koje se može videti da sadržaj arsena u odvodnoj vodi ima uglavnom konstantnu vrednost koja je manja od 5 u.g/1. In this example, a groundwater composition model is passed through a filtration unit, where the filtration unit contains sand coated with iron hydroxide. The depth of the filtration layer was 2.4 m and the filtration speed was 2 m/h. The composition of the groundwater that served as a liquid model had the following content of arsenic (V) = 250 ± 50 u.g/1, P04 " = 0.25 ± 0.10 mg as P and HC03" = 250 ± 20 mg/l, with a pH value of 7.7. The result is shown graphically in Figure 2, from which it can be seen that the content of arsenic in the drainage water has a mostly constant value, which is less than 5 u.g/1.

Primer 3 Example 3

U cilju određivanja profila uklanjanja arsena korišćena je filtraciona kolona koja sadrži filtracioni medijum obložen hidroksidom gvožđa, naime pesak iz postojećeg postrojenja za preradu podzemne vode, kao i model kompozicija podzemne vode. Kompozicija podzemne vode bila je sledeća: arsen As (V) = 250 ± 50 u.g/1, HCO3" = 250 ± 20 mg/l, sa pH vrednošću 7.7 ± 0.2. Brzina filtracije bila je 5 m/h i dubina sloja 2.3 m. Eksperimentalni podaci su grafički prikazani na Slici 3, na kojoj se može videti da se visok stepen uklanjanja arsena postiže čak i posle 14 postupaka regeneracije (obnavljanja). In order to determine the arsenic removal profile, a filtration column containing a filtration medium coated with iron hydroxide, namely sand from the existing groundwater treatment plant, was used, as well as a model of the groundwater composition. The composition of the groundwater was as follows: arsenic As (V) = 250 ± 50 u.g/1, HCO3" = 250 ± 20 mg/l, with a pH value of 7.7 ± 0.2. The filtration speed was 5 m/h and the depth of the layer 2.3 m. The experimental data are shown graphically in Figure 3, where it can be seen that a high degree of arsenic removal is achieved even after 14 procedures regeneration (renewal).

Primer 4 Example 4

Model kompozicije podzemne vode, koja sadrži arsen As (V) - 205 ± 50 u.g/1, HCO3' = 250 ± 20 mg/l, propuštan je kroz filtracionu jedinicu sa brzinom filtracije od 5 m/h i dubinom filtracionog sloja od 2.3 m. Rezultati eksperimenta, sa sadržajem arsena koji je određivan na različitim položajima duž filtracione jedinice, prikazani su na Slici 4, na kojoj se može videti da je sadržaj arsena u odvodnoj vodi uglavnom nezavisan od broja postupaka regeneracije (obnavljanja). The groundwater composition model, which contains arsenic As (V) - 205 ± 50 u.g/1, HCO3' = 250 ± 20 mg/l, was passed through a filtration unit with a filtration speed of 5 m/h and a filtration layer depth of 2.3 m. The results of the experiment, with the arsenic content determined at different positions along the filtration unit, are shown in Figure 4, where it can be seen that the arsenic content in the drainage water is mostly independent of the number of regeneration procedures.

Primer 5 Example 5

Voda koja ima početni sadržaj olova od 4 g/l i početni sadržaj kadmijuma, nikla, bakra i hroma od po 2 mg/l, podvrgnuta je adsorpcionim eksperimentima. Rezultati eksperimenata su grafički prikazani na Slici 5, na kojoj se može videti da su se sadržaji teških metala u odvodnoj vodi značajno smanjili posle perioda kontakta od oko 5 dana. Water with an initial lead content of 4 g/l and an initial content of cadmium, nickel, copper and chromium of 2 mg/l was subjected to adsorption experiments. The results of the experiments are shown graphically in Figure 5, where it can be seen that the contents of heavy metals in the drainage water significantly decreased after a contact period of about 5 days.

Claims

1. A process for removing metals from water containing metals, in which said water is brought into contact with a carrier material, where the carrier material functions as an adsorption medium for metals, wherein the process includes the following stages (phases): a) providing a filtration medium already coated with iron hydroxide as a carrier material, b) bringing the carrier material obtained in stage a) into contact with water so as to obtain drainage water, c) stopping stage b) when the metal content in drainage water exceeds a certain value, d) regeneration (restoration) of the carrier material from stage c), and if possible e) repetition of stage b)-d), characterized by the fact that the mentioned stage d) of regeneration (renewal) is performed by bringing the mentioned support material into contact with the Fe(II) solution.

2. The method according to patent claim 1, characterized in that the filtration medium coated with iron hydroxide is selected from the group consisting of sand, pumice stone, anthracite or their combination.

3. The method according to patent claim 2, characterized by the fact that sand from the existing groundwater treatment plant was used.

4. The method according to claim 1, characterized in that steps a)-d) are carried out in the same container.

5. The method according to patent claim 1, indicated by the fact that the carrier material is washed with water after regeneration according to the procedure from step d), so that the iron flakes formed during said regeneration are removed.

6. The method according to patent claim 1, characterized in that step b) is performed in such a way that the carrier material behaves as a stationary layer.

7. The method according to patent claim 1, indicated by the fact that stage b) is performed in such a way that water is passed in an upward direction through the layer of carrier material.

8. The method according to patent claim 1, characterized by the fact that the carrier material according to step a) has an average diameter of 0.8-5.0 mm.

9. The procedure according to patent claim 1, indicated by the fact that the speed of water filtration in stage b) is 0.5-20.0 m/h.

10. The method according to patent claim 1, indicated by the fact that the total depth of the carrier material layer is 0.5-4.0 m.