DK151375B - PROCEDURE FOR REMOVAL OF MERCURY OIL FROM ACID INDUSTRIAL WASTE WATER - Google Patents
PROCEDURE FOR REMOVAL OF MERCURY OIL FROM ACID INDUSTRIAL WASTE WATER Download PDFInfo
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- DK151375B DK151375B DK545381A DK545381A DK151375B DK 151375 B DK151375 B DK 151375B DK 545381 A DK545381 A DK 545381A DK 545381 A DK545381 A DK 545381A DK 151375 B DK151375 B DK 151375B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G13/00—Compounds of mercury
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B43/00—Obtaining mercury
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/043—Treatment of partial or bypass streams
Description
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Den foreliggende opfindelse angår en fremgangs-måde til fjernelse af kviksølv fra surt industrielt spildevand indeholdende kemisk bundet kviksølv, ved hvilken fremgangsmåde der gøres brug af kendt udfældning 5 af det tilstedeværende kviksølv i sulfidform ved behandling med et overskud af natriumsulfid i nærværelse af et flokkulationsmiddel, idet der benyttes alkaliske betingeler, med en pH-værdi beliggende mellem 7 og 12, og hvilken fremgangsmåde er ejendommelig Ved det i 10 kravets kendetegnende del anførte.The present invention relates to a process for removing mercury from acidic industrial wastewater containing chemically bonded mercury, using a method of using known precipitate 5 of the present mercury in sulphide form by treating with an excess of sodium sulphide in the presence of a flocculant. using alkaline conditions having a pH value between 7 and 12 and which method is peculiar to the characterizing part of claim 10.
Det er velkendt, hvor vigtigt problemet med kviksølvforurening er, navnlig efter at der har været konstateret meget alvorlige forgiftningstilfælde, hvoraf nogle med dødelig udgang, og efter at der er konstateret til-15 stedeværelse af store mængder kviksølv i kød fra fisk, som er fanget i områder, der er kraftigt forurenet med kviksølvholdigt spildevand.It is well-known how important the problem of mercury pollution is, especially after very serious cases of poisoning, some of which have been fatal, and after the presence of large quantities of mercury in meat from fish caught in areas heavily contaminated with mercury-containing wastewater.
Problemets alvor har ført til, at regeringerne i de vigtigste industrilande har stillet strenge krav til 20 nedsættelse af kviksølvindholdet, både i form af metal og som forbindelser, i industrielle spildprodukter, navnlig dem i væskeform.The seriousness of the problem has led the governments of the main industrialized countries to impose strict requirements on reducing the mercury content, both in the form of metal and as compounds, in industrial waste products, especially those in liquid form.
I Italien er den tilladte maksimumgrænse på 5 mikrogram pr.liter.In Italy, the maximum permitted limit is 5 micrograms per liter.
25 En af de væsentligste kilder til vandforurening med kviksølv menes at være processen til elektrolytisk fremstilling af chlor, der gør brug af kviksølvceller, og herefter følger de katalytiske processer, der gør brug af kviksølvsalte som katalysatorer for organiske synteser, 30 såsom fremstillingen af acetaldehyd og vinylchlorid ud fra acetylen.One of the major sources of water pollution by mercury is believed to be the process of electrolytic production of chlorine using mercury cells, followed by the catalytic processes which use mercury salts as catalysts for organic syntheses, such as the preparation of acetaldehyde and vinyl chloride from acetylene.
De industrier, der er tale om, har gjort sig store anstrengelser for at løse problemet, og der er foreslået adskillige metoder til at nedsætte kviksølvindholdet i 2 151375 industrielt spildevand til de af de nye love foreskrevne værdier.The industries in question have made great efforts to solve the problem and several methods have been proposed to reduce the mercury content of industrial waste water to the values prescribed by the new laws.
Hvor der er tale om metallisk kviksølv, er der således blevet benyttet specielle filtreringstrin, såsom 5 med aktiveret trækul, eller dannelse af metalliske amalgamer, mens der til bundet kviksølv er gjort brug af fældning, adsorption på ionbytterharpikser, reduktion til elementært kviksølv og andre kemiske og elektrokemiske metoder.Thus, in the case of metallic mercury, special filtration steps, such as 5 with activated charcoal, or formation of metallic amalgams have been used, while precipitation has been used for bonded mercury, adsorption on ion exchange resins, reduction to elemental mercury and other chemical and electrochemical methods.
10 Blandt udfældningsmetoderne er den mest benyttede den metode, der fører til dannelse af mercurisulfid. Denne metode gennemføres i almindelighed ved at behandle det med kviksølvforbindelser forurenede spildevand med opløsninger af natriumsulfid eller hydrosulfit, ved en pH-vær-15 di på ca. 8, idet der foretages flakkulation af det herved dannede kolloidale bundfald med for eksempel ferri-chlorid, eller med et hvilket som helst andet egnet flok-kulationsmiddel, efterfulgt, efter dekantering, af filtrering af det dannede slam.10 Among the precipitation methods, the most widely used is the method which leads to the formation of mercuric sulfide. This method is generally carried out by treating the waste water contaminated with mercury with solutions of sodium sulphide or hydrosulphite, at a pH of approx. 8, flocculating the colloidal precipitate thus formed with, for example, ferric chloride, or with any other suitable flocculant followed by decantation of filtration of the resulting sludge.
20 En fremgangsmåde som ovenfor nævnt har imidlertid nogle få ulemper. For at opnå en så kvantitativ udfældning af kviksølv som muligt er det nødvendigt at anvende et stort overskud af natriumsulfid, og natriumsulfid har en tendens til at hydrolysere med deraf følgende udvik-25 ling af hydrogensulfid, der i sig selv er meget toxisk.However, a method as mentioned above has a few drawbacks. In order to obtain as quantitative precipitation of mercury as possible, it is necessary to use a large excess of sodium sulphide, and sodium sulphide tends to hydrolyze with the resulting evolution of hydrogen sulphide which is very toxic in itself.
Endvidere indebærer anvendelsen af ferrichlorid som flokkulationsmiddel problemet med dannelse af store mængder jernhydroxid, der er et meget voluminøst bundfald, som kun vanskeligt indsamles på filtre, og som foruden at 30 indebære problemet med forbrug af jernsalte også indebærer det yderligere og væsentligere problem med behandling af store mængder slam med lavt kviksølvindhold og tilsvarende meget højt procentindhold af fugtighed (op til 60% eller endog 70%).Furthermore, the use of ferric chloride as the flocculant involves the problem of forming large amounts of iron hydroxide, which is a very voluminous precipitate which is only difficult to collect on filters and which, in addition to the problem of consumption of iron salts, also involves the further and more substantial problem of treating iron salts. large amounts of sludge with low mercury content and correspondingly very high moisture content (up to 60% or even 70%).
35 Heller ikke anvendelse af ikke-ioniske flokkulati- onsmidler, der ganske vist ikke indebærer problemet med jernforbrug, løser problemet med slammasserne og vanskelighederne med at opsamle disse på filtre, filtrering og 3 151375 efterfølgende behandlinger.35 Nor does the use of non-ionic flocculants, which do not involve the problem of iron consumption, solve the problem of the sludge masses and the difficulty of collecting them on filters, filtration and subsequent treatments.
Filtrering af kolloidale bundfald foretages i almindelighed med rotationsfiltre udstyret med en dicalite-foring, der både er et bæreorgan og en filtreringshjælper, 5 hvorfra bundfaldet fjernes ved skrabning med en skraber. Dicalite-foringen hindrer beskadigelse af filtergitteret under fjernelsen af bundfaldet, men der konstateres altid fjernelse af dicalite, således at der ved filtrering sker et stadigt forbrug deraf.Colloidal precipitation filtration is generally carried out with rotary filters equipped with a dicalite liner, which is both a support and a filtration aid, from which the precipitate is removed by scraping with a scraper. The dicalite liner prevents damage to the filter grating during the removal of the precipitate, but removal of dicalite is always noted, so that through filtration there is a constant consumption thereof.
10 Det har nu vist sig, at de ovennævnte ulemper til en vis grad kan undgås, hvis der benyttes fremgangsmåden ifølge opfindelsen, der er af den indledningsvis nævnte art, og ved hvilken det ejendommelige består i, at det dannede alkaliske slam, efter afsætning, behandles med 15 en del af det endnu ikke for kviksølv befriede spildevand, i et mængdeforhold surt spildevand/alkalisk slam på fra lo:l til 20:1, til der er opnået en pH-værdi mellem 2,2 og 2,5, hvorefter denne spildevandsdel gencirkuleres til udfældningstrinnet med natriumsulfid efter fil-20 treringen.It has now been found that the above-mentioned drawbacks can be avoided to some extent if the method according to the invention, which is of the kind mentioned in the preamble, is used, and in which the peculiarity consists in the formation of the alkaline sludge, after deposition, treated with 15 a portion of the mercury-free wastewater, in an acidic wastewater / alkaline sludge ratio of from 1: 1 to 20: 1, to a pH of between 2.2 and 2.5, after which this wastewater portion is recycled to the sodium sulfide precipitation step after filtration.
Det har vist sig, at denne behandling gør det muligt at genopløse de amorfe stoffer, der er flokkuleret, hvorved der som rest fås mercurisulfidbundfaldet, det let kan opsamles på en sædvanlig filterpresse eller i hvert 25 fald uden nogen form for filterhjælp, såsom dicalite, og med et minimum af resterende fugtighed.It has been found that this treatment allows the flocculated amorphous substances to be redissolved to obtain as a residue the mercuric sulfide precipitate, it can easily be collected on a conventional filter press or at least without any filter aid, such as dicalite, and with a minimum of residual moisture.
Det herved vundne mercurisulfid er endvidere praktisk taget frit for grove urenheder, således at det kan anvendes direkte i ristningstrinnet til tilvejebrin-30 gelse af elementært kviksølv.Furthermore, the mercuric sulfide thus obtained is practically free from coarse impurities, so that it can be used directly in the roasting step to provide elemental mercury.
Fremgangsmåden ifølge opfindelsen belyses nærmere i det følgende, hvor der er beskrevet fældningsforsøg med kviksølvforbindelser indeholdt i spildevand, der stammer fra enheder til katalytisk syntese af vinylchlorid ud 35 fra acetylen. De her rapporterede forsøg er indledningsvis gennemført i laboratoriemålestok og derefter i enhe- 4 151375 der af industriel målestok.The process of the invention is elucidated in the following, in which precipitation experiments with mercury compounds contained in wastewater arising from units for catalytic synthesis of vinyl chloride out of acetylene are described. The experiments reported here were initially carried out on a laboratory scale and then on an industrial scale.
Endvidere henvises til tegningen, hvis figur vi-ser et blokdiagram over fremgangsmåden ifølge opfindelsen.Furthermore, reference is made to the drawing, whose figure shows a block diagram of the method according to the invention.
5 På tegningen er 1 en strøm af calciumhvdroxid- suspension, 2 er en vandig opløsning af flokkulations-middel, 3 er en strøm af spildevand, hvis kviksølvindhold skal nedbringes, 4 er en vandig opløsning af natriumsulfid, 5 er en reaktionsbeholder udstyret med en 10 omrører, og hvori der skal opretholdes en pH-værdi over 7-9, 6 er en afsætningstank, 7 er silicafiltre, 8 filtre med aktiveret trækul, gennem hvilke vandet, der endnu indeholder spor af mercurisulfid, bringes til at strømme, 9 er et udløb for kviksølv-befriet vand, 10 15 er en strøm af alkalisk slam, 11 er en opløsningsbeholder, hvortil en fraktion af strømmen 3 af det vand, der skal befries for kviksølv, ankommer, 14 er en filterpresse eller andet direkte filtreringssystem, 12 er en gencirkuleret strøm af det vand, der skal befries 20 for kviksølv, og 13 er et ved filtrering vundet surt og fugtigt slam.5 In the drawing, 1 is a stream of calcium hydroxide suspension, 2 is an aqueous solution of flocculant, 3 is a stream of sewage whose mercury content is to be reduced, 4 is an aqueous solution of sodium sulfide, 5 is a reaction vessel equipped with a 10 stirrer, and maintaining a pH above 7-9, 6 is a deposition tank, 7 are silica filters, 8 activated charcoal filters through which the water still containing traces of mercuric sulfide is made to flow, 9 is a outlet for mercury-liberated water, 10 15 is a stream of alkaline sludge, 11 is a solution container to which a fraction of stream 3 of the water to be liberated for mercury arrives, 14 is a filter press or other direct filtration system, 12 is a recirculated stream of the water to be liberated 20 from mercury, and 13 is an acidic and moist sludge obtained by filtration.
EksempelExample
Det fra vinylchloridsynteseanlægget kommende spil-25 devand er surt, med en pH-værdi på ca. 1,8, og indeholder kviksølvforbindelser i en mængde, der nærmer sig 10 milligram pr.liter. For at opfylde de lovmæssige krav skal kviksølvindholdet nedsættes til højst 5 mikrogram pr.liter .The spill-25 devand coming from the vinyl chloride synthesis plant is acidic, with a pH of approx. 1.8, and contains mercury compounds in an amount approaching 10 milligrams per liter. In order to meet the legal requirements, the mercury content must be reduced to a maximum of 5 micrograms per liter.
Ved laboratorieforsøg blev sådant vand under omrøring behandlet med kalkmælk (en vandig opslæmning af kalk) for at gøre det alkalisk, indtil en pH-værdi på ca.In laboratory experiments, such stirred water was treated with lime milk (an aqueous slurry of lime) to make it alkaline, until a pH of approx.
10 var nået, og samtidigt blev der pr.liter tilsat 5 ml af en vandig opløsning af et polyacrylamid-baseret, ikke-35 ionisk flokkulationsmiddel (Prodefloc N2M, varemærke for PRODECO Company) med en koncentration på 1 gram pr.liter.10 was reached and at the same time 5 ml of an aqueous solution of a polyacrylamide-based, nonionic flocculant (Prodefloc N2M, trademark of PRODECO Company) was added at a concentration of 1 gram per liter.
Derefter blev der tilsat en vandig opløsning af natriumsulfid, med en koncentration på 5 gram pr.liter, i 5 151375 en mængde, der var tre gange den støkiometriske mængde af kviksølv, og omrøring blev fortsat i ca. 1 time. Omrøring blev derefter afbrudt for at lade bundfaldet afsætte sig.Then, an aqueous solution of sodium sulfide, at a concentration of 5 grams per liter, was added in an amount three times the stoichiometric amount of mercury, and stirring was continued for approx. 1 hour. Stirring was then discontinued to allow the precipitate to settle.
Efter 3 timers henstand blev det overliggende klare 5 vand udtrukket og sendt til filtreringstrinnet på aktiveret trækul, på hvilket det resterende mercurisulfidindhold blev fraskilt.After standing for 3 hours, the supernatant clear water was extracted and sent to the filtration step on activated charcoal, to which the remaining mercuric sulfide content was separated.
Mercurisulfidindholdet, der i vandet fra afsætningen var på lidt under 100 mikrogram pr.liter, var efter filtrering 10 nedsat til værdier på fra 2 til 5 mikrogram pr.liter.The mercury sulphide content, which in the water from the deposit was slightly below 100 micrograms per liter, after filtration was reduced to values of 2 to 5 micrograms per liter.
Det alkaliske slam fra afsætningstanken blev i mellemtiden overført til en opløsningsbeholder, hvori en del af det spildevand, der skulle befries for kviksølv, blev indført som sådant (dvs. med en pH-værdi på ca. 1,8), 15 indtil der var nået en pH-værdi beliggende mellem 2,2 og 2,5. På dette trin var ca. 80% af slammet opløst, mens der som uopløst materiale, i form af et tungt bundfald, kun var efterladt kviksølvsulfiderne og sulfiderne af de i vandet eventuelt tilstedeværende metaller fra 1. og 2.Meanwhile, the alkaline sludge from the deposit tank was transferred to a solution vessel in which a portion of the wastewater to be liberated from mercury was introduced as such (ie, with a pH of about 1.8) until reached a pH value between 2.2 and 2.5. At this stage, approx. 80% of the sludge dissolved, while as unresolved material, in the form of a heavy precipitate, only the mercury sulphides and sulphides of the metals present in the water from 1st and 2nd were left behind.
20 Gruppe.20 group.
Det resterende bundfald blev hensigtsmæssigt indsamlet på et filter i vakuum, på et filterklæde, uden noget behov for en dicalite-filterhjælp.The remaining precipitate was conveniently collected on a filter in vacuum, on a filter cloth, without any need for a dicalite filter aid.
Det vandige filtrat, der endnu indeholdt kviksølv-25 forbindelser, blev gencirkuleret til natriumsulfidbehandlingen.The aqueous filtrate, which still contained mercury compounds, was recycled for the sodium sulfide treatment.
Det på filtret opsamlede bundfald, der udgjorde ca.The precipitate collected on the filter, which amounted to approx.
0,1 gram pr.liter behandlet vand, havde et indhold på ca.0.1 grams per liter of treated water, had a content of approx.
10% kviksølv, udtrykt som elementært metal.10% mercury, expressed as elemental metal.
30 Forsøg i industriel målestok blev gennemført med brug af samme trinfølge som i laboratoriet.Thirty industrial scale experiments were performed using the same step sequence as in the laboratory.
I stedet for glasapparatur i forstørret dimension blev der anvendt metalliske materialer.Instead of enlarged dimension glass appliances, metallic materials were used.
Dimensionerne af det industrielle apparatur var: 35 Reaktionsbeholder 5 (beholder, hvori væsken blev gjort al- 3 3 kalisk): ca. 300 m , flokkulationsbeholder 6: ca. 120 m , 3 filter 8 med aktiveret trækul: 3 m , opløsningsbeholder 3 11 for alkalisk slam: 3 m .The dimensions of the industrial apparatus were: 35 Reaction vessel 5 (vessel in which the liquid was made alkaline 3): approx. 300 m, flocculation container 6: approx. 120 m, 3 filter 8 with activated charcoal: 3 m, solution container 3 11 for alkaline sludge: 3 m.
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Ved den industrielle proces blev endvidere den neutraliserende kalkmælk tilsat med et doseringsorgan, indtil der var nået en pH-værdi på 8-9. Opløsningen, der var gjort alkalisk, blev ledt til flokkulationsapparatet, 5 hvortil der også blev sat natriumsulfid (i en mængde 3 gange den støkiometriske mængde, der krævedes til udfældning af mercurisulfid, således at også andre eventuelt tilstedeværende metaller blev udfældet), og forud var tilført det ikke-ioniske flokkulationsmiddel.In the industrial process, furthermore, the neutralizing lime milk was added with a dosing means until a pH of 8-9 was reached. The alkaline solution was passed to the flocculator, to which was also added sodium sulfide (3 times the stoichiometric amount required to precipitate mercuric sulfide, so that any other metals present) precipitated as well. applied to the nonionic flocculant.
10 Det blev konstateret, at forbruget af flokkulati- onsmiddel ved det industrielle forsøg var det halve af forbruget konstateret ved laboratorieforsøget.10 It was found that the consumption of flocculant in the industrial experiment was half that of the laboratory test.
Eventuelt resterende overskud af natriumsulfid blev adsorberet af filtret med aktiveret trækul.Any residual excess sodium sulfide was adsorbed by the activated charcoal filter.
15 Efter afsætning blev det flokkulerede slam sendt til opløsningsbeholderen, mens det klare vand blev sendt til filtret med aktiveret trækul.After deposition, the flocculated sludge was sent to the solution vessel while clear water was sent to the activated charcoal filter.
Det fra flokkulations-afsætningsbeholderen kommende vand havde et kviksølvindhold beliggende mellem 50 og 200 20 mikrogram pr.liter. Efter adsorption på filtret med aktiveret trækul var den gennemsnitlige koncentration af kviksølv i det udtrædende vand nedsat til værdier beliggende mellem 2 og 5 mikrogram pr.liter.The water coming from the flocculation container had a mercury content of between 50 and 200 to 20 micrograms per liter. After adsorption on the activated charcoal filter, the average concentration of mercury in the effluent was reduced to values between 2 and 5 micrograms per liter.
For at hindre svømmende fnug i at tilstoppe filtret 25 med aktiveret trækul var et silicafilter indsat før trækulsfiltret.In order to prevent swimming fluff from clogging the activated charcoal filter 25, a silica filter was inserted before the charcoal filter.
Det slam, der førtes til opløsningsbeholderen, blev behandlet med det vand, der skulle befries for kviksølv.The sludge conveyed to the dissolution vessel was treated with the water to be liberated from mercury.
Forholdet mellem surt vand og alkalisk slam er en 30 funktion af vandets pH-værdi og koncentrationen af faste stoffer opslæmmet i slammet og ligger i området fra 10:1 til 20:1.The ratio of acidic water to alkaline sludge is a function of the pH of the water and the concentration of solids suspended in the sludge and ranges from 10: 1 to 20: 1.
Efter hvert opløsningstrin fik det syrnede slam lov at afsætte sig for at muliggøre udtrækning af vandet 35 ved hævertvirkning.After each dissolution step, the acidified sludge was allowed to settle to allow extraction of the water 35 by siphoning action.
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Vandet blev gencirkuleret til reaktionsbeholderen.The water was recycled to the reaction vessel.
Det sure slam fra opløsningsbeholderen blev sendt til filtreringstrinnet i en filterpresse, hvorved dannedes en kompakt filterkage, der let kunne fjernes fra filterdugen.The acidic sludge from the solution container was sent to the filtration step in a filter press, forming a compact filter cake that could be easily removed from the filter cloth.
5 Forsøg med kviksølvfjernelse er med henblik på sam menligning også foretaget på samme spildevand, men uden behandling af det alkaliske slam med det vand, der skulle befries for kviksølv.5 For the purpose of comparison, experiments with mercury removal were also carried out on the same wastewater, but without treatment of the alkaline sludge with the water to be liberated from mercury.
Den væsentligste forskel var nødvendigheden af dag-ligt at måtte kassere afsætningstanken og filtrere det alkaliske slam, da sidstnævnte var meget voluminøst, mens det ved forsøgene omfattende opløsningstrinnet var tilstrækkeligt, og ikke absolut nødvendigt, at foretage filtreringen ugentligt.The main difference was the necessity of daily disposing of the deposit tank and filtering the alkaline sludge, as the latter was very voluminous, while the filtration step comprising the dissolution step was sufficient, and not absolutely necessary, to do the filtration weekly.
15 Regenereringen af filtret med aktiveret trækul blev foretaget in situ efter mere end 45 dages operation, ved udludning med en 3% saltsyreopløsning, hvortil der var sat et korrosionshæmmende middel.The regeneration of the activated charcoal filter was carried out in situ after more than 45 days of operation, by leaching with a 3% hydrochloric acid solution to which a corrosion inhibitor was added.
I de følgende tabeller er samlet data stammende fra 2Q en række forsøg gennemført i overensstemmelse med den ovenfor beskrevne fremgangsmåde, og til sammenligning er også forsøg gennemført uden slambehandling rapporteret i tabellerne. Værdierne for kviksølvindholdet i det vand, der skulle behandles, og i det fra filtret med aktiveret 25 trækul kommende vand er anført for begge tilfælde, ligesom slammængderne, deres respektive kviksølvindhold og andre data.In the following tables, overall data from 2Q are a series of experiments conducted in accordance with the procedure described above, and by comparison, experiments conducted without sludge treatment are also reported in the tables. The values for the mercury content in the water to be treated and in the activated charcoal water filter are listed for both cases, as are the amounts of sludge, their respective mercury content and other data.
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Tabel ITable I
Kviksølvindhold i vandet til og fra anlægget til kviksølvfjernelse.Mercury content in the water to and from the plant for mercury removal.
55
Kviksølvindhold i vand i mikrogram pr.literMercury content in water in micrograms per liter
For- Indgående Bortgående I Bortgående til behand- fra flokku- ; fra filter søg lingsanlæg lations- j med akti- nr. beholder ; veret trækul 10 ΓΤ ---Pro- Incoming Disposal I Disposal for treatment of flocculus; from filter search system lationsj with stock container; veret charcoal 10 ΓΤ ---
Labora- i 5.900 65 4,0 torie- 2 8.400 80 4,6 3 6-500 40 3,6 forsøg 4 10.600 35 2,2 5 4.000 83 6,0 η c Indu— 8 1.600 20 3,0 15 7 2.100 39 3,6 strielle 8 1.100 78 2,1 forsøg 9 3-400 60 3,7 10 3.600 37 3,2 11 3,400 83 2,9 12 8.000 95 4,0 9 151375Laboratory 5,900 65 4.0 theory 2 8,400 80 4.6 3 6-500 40 3.6 Trials 4 10,600 35 2.2 5 4,000 83 6.0 η c Indu- 8 1,600 20 3,0 15 7 2,100 39 3.6 Striels 8 1,100 78 2.1 Trials 9 3-400 60 3.7 10 3,600 37 3.2 11 3,400 83 2.9 12 8,000 95 4.0 9 151375
Tabel IITable II
Egenskaber af slam vundet ved fældning af kviksølv i spildevand.Properties of sludge gained by precipitation of mercury in wastewater.
5 ___5 ___
Sammensætning af slam efter fil-Sludge composition by file
Forsøg -,-Coring (vægti)- Mængde Fug- Analyse på våde prøver (vægt%) r ’ kg/rn^ tig hed Kviksølv Jern Calcium in Labora- 1 0,05 50 8,90 4,56 5,28 . . _ 2 0,06 55 9,5 3,85 4,85 torxe 3 o,048 51 8,85 4,2 5,3 forsøg 4 , 0,051 53 10,5 3,6 5,0 13 0,38 72 3,33 3,26 6,24 141 0,311 74 1,75 2,85 5,8 151{ 0,4 68 2,5 3,3 4,2 161 0,35 60 3,2 2,80 5,0 15-------Experiment - Coring (wt) - Amount of Moisture Analysis on Wet Samples (wt%) r 'kg / hr Mercury Iron Calcium in Labora- 1 0.05 50 8.90 4.56 5.28. . 2 0.06 55 9.5 3.85 4.85 Torx 3 0.48 51 8.85 4.2 5.3 Experiment 4, 0.051 53 10.5 3.6 5.0 13 0.38 72 3 , 33 3.26 6.24 141 0.311 74 1.75 2.85 5.8 151 {0.4 68 2.5 3.3 4.2 161 0.35 60 3.2 2.80 5.0 15 -------
Indu- 5 0,056 52 9,2 4,25 5,35 6 0,04 48 10,1 4,00 4,95Induction 0.056 52 9.2 4.25 5.35 6 0.04 48 10.1 4.00 4.95
Stri 7 0,048 50 8,9 3,25 5,00 elle 8 0,060 53 9,9 3,80 5,20 - 9 0,050 50 8,95 3,90 5,40 fors0g 10 0,042 52 8,4 4,15 4,8 20 11 0,055 51 9,2 3,95 5,3 12 . 0,051 49 10,3 4,30 4,9 171 0,311 71 2,2 2,9 5,5 181 0,330 70 1,8 3,2 4,9 191 0,295 68 2,3 2,85 5,8 201 0,300 65 3,2 2,7 6,2 211 0,350 69 3,5 3,5 4,5 221 0,310 64 2,9 3,3 5,9 25 231 0,298 60 3,35 2,95 5,0 241' 0,308 65 2,85 3,00 4,8 35 )Stri 7 0.048 50 8.9 3.25 5.00 or 8 0.060 53 9.9 3.80 5.20 - 9 0.050 50 8.95 3.90 5.40 Attempt 10 0.042 52 8.4 4.15 4 , 8 20 11 0.055 51 9.2 3.95 5.3 12. 0.051 49 10.3 4.30 4.9 171 0.311 71 2.2 2.9 5.5 181 0.330 70 1.8 3.2 4.9 191 0.295 68 2.3 2.85 5.8 201 0.300 65 3.2 2.7 6.2 211 0.350 69 3.5 3.5 4.5 221 0.310 64 2.9 3.3 5.9 25 231 0.298 60 3.35 2.95 5.0 241 0.308 65 2.85 3.00 4.8 35)
De således mærkede forsøg angår fældning af kviksølv som sulfid uden efterfølgende behandling af slam med en fraktion af det vand, der skulle befries for kvik-30 sølv.The tests thus marked relate to the precipitation of mercury as sulphide without subsequent treatment of sludge with a fraction of the water to be liberated from mercury.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2656380 | 1980-12-11 | ||
| IT26563/80A IT1134671B (en) | 1980-12-11 | 1980-12-11 | PROCEDURE FOR THE DISPOSAL OF MERCURY FROM WASTE WATER |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK545381A DK545381A (en) | 1982-06-12 |
| DK151375B true DK151375B (en) | 1987-11-30 |
| DK151375C DK151375C (en) | 1988-05-16 |
Family
ID=11219786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK545381A DK151375C (en) | 1980-12-11 | 1981-12-09 | PROCEDURE FOR REMOVAL OF MERCURY OIL FROM ACID INDUSTRIAL WASTE WATER |
Country Status (11)
| Country | Link |
|---|---|
| BE (1) | BE891432A (en) |
| CH (1) | CH652707A5 (en) |
| DE (1) | DE3147549C2 (en) |
| DK (1) | DK151375C (en) |
| ES (1) | ES508225A0 (en) |
| FR (1) | FR2496083A1 (en) |
| GB (1) | GB2089335B (en) |
| IT (1) | IT1134671B (en) |
| NL (1) | NL8105594A (en) |
| NO (1) | NO154010C (en) |
| SE (1) | SE444807B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE58904374D1 (en) * | 1988-01-14 | 1993-06-24 | Siemens Ag | METHOD AND DEVICE FOR PURIFYING SMOKE GASES. |
| AU617166B2 (en) * | 1988-03-31 | 1991-11-21 | Commonwealth Scientific And Industrial Research Organisation | Hydrometallurgical effluent treatment |
| WO1989009192A1 (en) * | 1988-03-31 | 1989-10-05 | Commonwealth Scientific And Industrial Research Or | Hydrometallurgical effluent treatment |
| DE4102972A1 (en) * | 1991-02-01 | 1992-08-13 | Ubib Unternehmensberatungs Gmb | METHOD AND DEVICE FOR RECYCLING LAMINATED LAMPS |
| FI97290C (en) * | 1994-12-30 | 1996-11-25 | Kemira Chemicals Oy | Method for treating sewage sludge |
| CN106621778B (en) * | 2016-12-29 | 2019-08-02 | 江苏新世纪江南环保股份有限公司 | The method and device of ammonia process of desulfurization slurries demercuration |
| CN114538656B (en) * | 2022-02-23 | 2023-12-22 | 湖北楚星化工股份有限公司 | Device and method for controlling addition amount of mercury removing agent in mercury-containing wastewater treatment |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1593761A1 (en) * | 1967-02-04 | 1972-04-13 | Basf Ag | Process for the separation of mercury from reaction mixtures of the anthraquinone sulfonation |
| CH543455A (en) * | 1971-06-21 | 1973-10-31 | Mueller Hans | Process for removing mercury from waste water |
| US3740331A (en) * | 1971-06-23 | 1973-06-19 | Sybron Corp | Method for precipitation of heavy metal sulfides |
| US3790370A (en) * | 1971-12-23 | 1974-02-05 | Univ Sherbrooke | Removal and recovery of metals from polluted waters |
| CH618148A5 (en) * | 1975-06-26 | 1980-07-15 | Schaefer Chemisches Inst Ag | Process for separating out heavy metal ions from the aqueous solutions of complex compounds of metal-sequestering and metal chelate-forming chemicals |
-
1980
- 1980-12-11 IT IT26563/80A patent/IT1134671B/en active
-
1981
- 1981-12-01 CH CH7693/81A patent/CH652707A5/en not_active IP Right Cessation
- 1981-12-01 DE DE3147549A patent/DE3147549C2/en not_active Expired
- 1981-12-01 GB GB8136195A patent/GB2089335B/en not_active Expired
- 1981-12-09 DK DK545381A patent/DK151375C/en active
- 1981-12-09 NO NO814193A patent/NO154010C/en unknown
- 1981-12-09 FR FR8123054A patent/FR2496083A1/en active Granted
- 1981-12-10 ES ES508225A patent/ES508225A0/en active Granted
- 1981-12-10 BE BE0/206799A patent/BE891432A/en not_active IP Right Cessation
- 1981-12-10 SE SE8107419A patent/SE444807B/en not_active IP Right Cessation
- 1981-12-11 NL NL8105594A patent/NL8105594A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| IT1134671B (en) | 1986-08-13 |
| SE8107419L (en) | 1982-06-12 |
| NO154010B (en) | 1986-03-24 |
| ES8300646A1 (en) | 1982-11-01 |
| FR2496083B1 (en) | 1984-12-28 |
| GB2089335A (en) | 1982-06-23 |
| DK151375C (en) | 1988-05-16 |
| SE444807B (en) | 1986-05-12 |
| NO814193L (en) | 1982-06-14 |
| IT8026563A0 (en) | 1980-12-11 |
| NL8105594A (en) | 1982-07-01 |
| BE891432A (en) | 1982-06-10 |
| NO154010C (en) | 1986-07-02 |
| CH652707A5 (en) | 1985-11-29 |
| ES508225A0 (en) | 1982-11-01 |
| DE3147549A1 (en) | 1982-06-24 |
| GB2089335B (en) | 1983-06-22 |
| DK545381A (en) | 1982-06-12 |
| DE3147549C2 (en) | 1983-10-20 |
| FR2496083A1 (en) | 1982-06-18 |
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