NO154010B - PROCEDURE FOR AA REMOVAL MERCURY OIL FROM SOURCE INDUSTRIAL WASTE WATER. - Google Patents
PROCEDURE FOR AA REMOVAL MERCURY OIL FROM SOURCE INDUSTRIAL WASTE WATER. Download PDFInfo
- Publication number
- NO154010B NO154010B NO814193A NO814193A NO154010B NO 154010 B NO154010 B NO 154010B NO 814193 A NO814193 A NO 814193A NO 814193 A NO814193 A NO 814193A NO 154010 B NO154010 B NO 154010B
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- Norway
- Prior art keywords
- mercury
- waste water
- sludge
- water
- filter
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 13
- 239000010842 industrial wastewater Substances 0.000 title claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 34
- 229910052753 mercury Inorganic materials 0.000 claims description 31
- 239000010802 sludge Substances 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 15
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000002351 wastewater Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000002731 mercury compounds Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G13/00—Compounds of mercury
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for å The present invention relates to a method for
fjerne kvikksølv fra surt, industrielt avløpsvann som inneholder kjemisk bundet kvikksølv, ved omsetning med et overskudd av natriumsulfid i nærvær av et flokkuleringsmiddel, idet utfelling gjennomføres ved en pH-verdi fra 7 til 12 og det erholdte alkaliske slam oppsamles etter avsetningen. Oppfinnelsen er karakterisert ved at slammet behandles med 10 til 20%, regnet på den totale mengde av det sure avløpsvann hvorfra kvikksølvet ennå ikke er fjernet, til det oppnår en pH-verdi fra 2,2 til 2,5, og det behandlede avløpsvann til-bakeføres etter filtrering av slammet til trinnet med utfellingen med natriumsulfid. remove mercury from acidic, industrial waste water containing chemically bound mercury, by reaction with an excess of sodium sulphide in the presence of a flocculating agent, precipitation being carried out at a pH value from 7 to 12 and the resulting alkaline sludge collected after deposition. The invention is characterized in that the sludge is treated with 10 to 20%, calculated on the total quantity of the acidic waste water from which the mercury has not yet been removed, until it reaches a pH value of 2.2 to 2.5, and the treated waste water to - fed back after filtering the sludge to the stage with the precipitation with sodium sulphide.
Viktigheten av å fjerne forurensning med kvikksølv er vel The importance of removing contamination with mercury is well known
kjent, spesielt etter at ytterst alvorlige tilfeller av for-giftning har vært påvist, enkelte av den endog med dødelig utgang, og etter at nærvær av store mengder kvikksølv er påvist i fiskekjøtt fra områder som var sterkt forurenset av kvikksølvholdig avløpsvann. known, especially after extremely serious cases of poisoning have been detected, some of them even fatal, and after the presence of large amounts of mercury has been detected in fish meat from areas that were heavily polluted by mercury-containing waste water.
Det store problem har ført til at myndighetene i de fleste viktige industriland har fastsatt ytterst strenge spesifika-sjoner for å redusere kvikksølvinnholdet, både i form av metall og i form av kvikksølvforbindelser i industrielle utstrømninger, spesielt i væskeform. I Italia er således den maksimale tillatte grense 5 mikrogram pr. liter. The major problem has led to the authorities in most important industrial countries having laid down extremely strict specifications to reduce the mercury content, both in the form of metal and in the form of mercury compounds in industrial effluents, especially in liquid form. In Italy, the maximum permissible limit is thus 5 micrograms per litres.
En av de viktigste kilder til vannforurensning; med kvikksølv anses å være fremgangsmåten for elektrolytisk fremstilling av klor hvor det anvendes kvikksølvceller, etterfulgt av de katalytiske prosesser hvor kvikksølvsalter anvendes som kata-lysatorer for organiske synteser, som f.eks. fremstilling av acetaldehyd og vinylklorid ved å gå ut fra acetylen. One of the most important sources of water pollution; with mercury is considered to be the method for the electrolytic production of chlorine where mercury cells are used, followed by the catalytic processes where mercury salts are used as catalysts for organic syntheses, such as e.g. production of acetaldehyde and vinyl chloride starting from acetylene.
De angjeldende industrier har gjort store anstrengelser for The relevant industries have made great efforts to
å løse disse problemer og flere metoder har vært foreslått for å redusere kvikksølvinnholdet i det industrielle avløpsvann til de verdier som er fastsatt i myndighetenes forskrifter. to solve these problems and several methods have been proposed to reduce the mercury content in the industrial waste water to the values laid down in the authorities' regulations.
For metallisk kvikksølv har man således forsøkt spesielle filtreringstrinn, f.eks. med aktivert trekull, eller for dannelse av metall-amalgamer, mens for kvikksølv i kombi- Special filtration steps have thus been tried for metallic mercury, e.g. with activated charcoal, or for the formation of metal amalgams, while for mercury in combi-
nert form har man forsøkt utfelling, adsorpsjon på ione-bytterharpikser, reduksjon til elementært kvikksølv og andre kjemiske og elektrokjemiske metoder. In this form, precipitation, adsorption on ion-exchange resins, reduction to elemental mercury and other chemical and electrochemical methods have been attempted.
Blant utfellingsmetodene er den som overveiende anvendes, Among the precipitation methods, the one that is predominantly used is,
den metode som fører til dannelse av Kvikksølv-sulfid. Denne metode gjennomføres vanligvis ved å behandle det vann som er forurenset med kvikksølvforbindelser med oppløsninger av natriumsulfid eller hydrosulfId, ved pH omtrent 8, med flokkulering av det derved dannede kolloidale bunnfall med f.eks. ferriklorid, eller med et annet passende flokkuleringsmiddel, etterfulgt av filtrering etter dekantering av de slam som er dannet. the method which leads to the formation of mercury sulphide. This method is usually carried out by treating the water which is contaminated with mercury compounds with solutions of sodium sulphide or hydrosulphide, at a pH of about 8, with flocculation of the colloidal precipitate thus formed with e.g. ferric chloride, or with another suitable flocculant, followed by filtration after decanting the sludges that have formed.
En metode av den ovennevnte type har imidlertid en del ulemper og for å komme så nær en kvantitativ utfelling av kvikksølv som mulig, kreves det faktisk anvendelse av et stort overskudd av natriumsulfid, idet natriumsulfid har tendens til hydrolyse med derav følgende utvikling av hydrogensulfid som i seg selv er meget giftig. However, a method of the above type has a number of disadvantages and in order to get as close to a quantitative precipitation of mercury as possible, the use of a large excess of sodium sulphide is actually required, as sodium sulphide tends to hydrolysis with the consequent development of hydrogen sulphide as in itself is highly toxic.
Videre medfører bruk av ferriklorid som flokkuleringsmiddel problemet med dannelse av store mengder jernhydroksyd som er et ytterst voluminøst bunnfall som samles på filtret med stor vanskelighet og som i tillegg til å medføre et annet problem, dvs. forbruk av jernsalter, frembyr det ytterligere og mer alvorlige problem med behandling av store masser av slam med lavt kvikksølvinnhold samtidig med en ytterst høy prosentandel fuktighet (opptil 60 eller endog 10%). Furthermore, the use of ferric chloride as a flocculating agent entails the problem of the formation of large amounts of iron hydroxide, which is an extremely voluminous precipitate that collects on the filter with great difficulty and which, in addition to causing another problem, i.e. the consumption of iron salts, produces further and more serious problem of treating large masses of sludge with a low mercury content at the same time as an extremely high percentage of moisture (up to 60 or even 10%).
Selv bruk av ikke-ioniske flokkuleringsmidler, selv om disse ikke frembyr problemet med jernforbruk, løser ikke problemet med det voluminøse slam og de vanskeligheter som følger med oppsamling av dette på filtret, filtrering og etterfølgende behandlinger. Even the use of non-ionic flocculants, although they do not present the problem of iron consumption, does not solve the problem of the voluminous sludge and the difficulties associated with its collection on the filter, filtration and subsequent treatments.
Filtrering av kolloidale bunnfall gjøres nå oftest med roterende filtre utstyrt med en foring av"dikalitt"som både er en understøttende del og et filtreringshjelpemiddel, hvorfra bunnfallet fjernes ved skraping med en såkalt doktorblad-kniv."Dikalitt-foringen forhindrer skader på filtergitteret under fjernelse av bunnfallet, men en fjernelse av"dikalitt" opptrer bestandig slik at et kontinuerlig forbruk derav foregår ved filtreringen. Filtration of colloidal precipitates is now most often done with rotary filters equipped with a lining of "dikalite" which is both a supporting part and a filtration aid, from which the precipitate is removed by scraping with a so-called doctor's blade knife." The dicalite lining prevents damage to the filter grid during removal of the sediment, but a removal of "dicalite" always occurs so that a continuous consumption of it takes place during the filtration.
Det er nå funnet at de ovennevnte ulemper kan avhjelpes i vesentlig grad hvis fremgangsmåten i henhold til oppfinnelsen følges. Denne skal beskrives mer detaljert i det følgende og omfatter trinnet med etter dekantering og underkaste det alkaliske slam som kommer fra utfellingen med natriumsulfid for innvirkning av en liten fraksjon ( fra 10 til 20% av den totale mengde ) av det vann som skal renses. Det er funnet at denne behandling gjør det mulig å gjenoppløse de amorfe substanser som flokkulerte og etterlater som en rest kvikksølv-sulf id-bunnfallet som lett kan samles på en konvensjonell filterpresse, eller i alle fall uten noen filterhjelpemidl-er som f.eks.''dikalitt'! og med en minimal restfuktighet. It has now been found that the above-mentioned disadvantages can be remedied to a significant extent if the method according to the invention is followed. This will be described in more detail in the following and includes the step of after decanting and subjecting the alkaline sludge that comes from the precipitation with sodium sulphide to the effect of a small fraction (from 10 to 20% of the total amount) of the water to be purified. It has been found that this treatment makes it possible to redissolve the amorphous substances that flocculated and leave as a residue the mercuric sulphide precipitate which can be easily collected on a conventional filter press, or in any case without any filter aids such as e.g. ''dicalite''! and with minimal residual moisture.
Det således oppnådde kvikksølv-sulfid er videre hovedsakelig fritt for grove forurensninger slik at det kan anvendes direkte i røste trinnet for oppnåelse av elementært kvikksølv. The mercuric sulphide thus obtained is further mainly free of coarse impurities so that it can be used directly in the roasting step for obtaining elemental mercury.
For at fremgangsmåten skal bli forklart bedre, skal det i In order for the procedure to be explained better, it must i
det følgende beskrives utfellingstester av kvikksølv-forbindelser inneholdt i avløpsvann som kommer fra enheter for katalytisk syntese av vinylklorid fra acetylen. De testene som er gjengitt heri, er i utgangspunktet foretatt i apparatur av laboratoriestørrelse og deretter i enheter med kommersiell størrelse. the following describes precipitation tests of mercury compounds contained in waste water coming from units for the catalytic synthesis of vinyl chloride from acetylene. The tests reproduced here were initially carried out in laboratory-sized equipment and then in commercial-sized units.
Den vedføyde tegning gjengir et blokkdiagram av fremgangsmåten The attached drawing shows a block diagram of the method
i henhold til oppfinnelsen. according to the invention.
I figuren vises en strøm 1 av suspensjon av kalsiumhydroksyd, In the figure, a stream 1 of suspension of calcium hydroxide is shown,
en strøm 2 av vandig oppløsning av flokkuleringsmiddel, en strøm 3 av vann som skal slippes ut etter at kvikksølvet er fjernet, videre en strøm 4 av en vandig oppløsning av a stream 2 of aqueous solution of flocculant, a stream 3 of water to be discharged after the mercury has been removed, further a stream 4 of an aqueous solution of
natriumsulfid, videre reaksjonsbeholderen 5 utstyrt med et røreverk og hvori pH 7-9 må opprettholdes, samt avsetnings-tank 6, silikafiltret 7, aktiverte trekullfiltre 8 hvori-gjennom det vann bringes til å strømme som fremdeles inneholder spor av kvikksølv-sulfid, utløp 9 for vann .hvorfra kvikksølv er fjernet, strømmen av alkalisk slam 10, opp-løsningsinnretning 11 hvortil en fraksjon av strømmen 3 sodium sulphide, further the reaction vessel 5 equipped with an agitator and in which pH 7-9 must be maintained, as well as settling tank 6, the silica filter 7, activated charcoal filters 8 through which water is made to flow which still contains traces of mercuric sulphide, outlet 9 for water from which mercury has been removed, the stream of alkaline sludge 10, dissolving device 11 to which a fraction of the stream 3
av vann hvorfra kvikksølvet skal fjernes, ankommer, samt endelig en filterpresse 14 eller annet direkte filtrerings-system, den re-sirkulerte strøm 12 av vann hvorfra kvikksølv skal fjernes og 13 er det sure og fuktige slam som oppnås ved filtrering. of water from which the mercury is to be removed arrives, as well as finally a filter press 14 or other direct filtration system, the re-circulated stream 12 of water from which the mercury is to be removed and 13 is the acidic and moist sludge obtained by filtration.
EKSEMPEL EXAMPLE
Det avløpsvann som kommer fra et synteseanlegg for vinylklorid er surt, med pH omtrent 1,8, og inneholder kvikksølvforbindelser i en mengde nær 10 mg/liter. For at de legale forskrifter skal etterkommes, må kvikksølvinnholdet reduseres til f.eks. høyst 5 mikrogram pr. liter. The wastewater coming from a vinyl chloride synthesis plant is acidic, with a pH of about 1.8, and contains mercury compounds in an amount close to 10 mg/liter. In order for the legal regulations to be complied with, the mercury content must be reduced to e.g. maximum 5 micrograms per litres.
Ved laboratorietester er slikt vann blitt behandlet under omrøring med kalkmelk (en vandig pulp av kalk) for å gjøre det alkalisk inntil det oppnås en pH på omtrent 10. Samtidig er det tilsatt 5 ml pr. liter av en vandig oppløsning av et polyakrylamid-basert ikke-ionisk flokkuleringsmiddel ("Prodefloc N2M"), med konsentrasjon 1 g/liter. In laboratory tests, such water has been treated while stirring with milk of lime (a watery pulp of lime) to make it alkaline until a pH of approximately 10 is achieved. At the same time, 5 ml per liters of an aqueous solution of a polyacrylamide-based non-ionic flocculant ("Prodefloc N2M"), with a concentration of 1 g/litre.
Deretter tilsettes en vandig oppløsning av natriumsulfid med An aqueous solution of sodium sulphide is then added
en konsentrasjon på 5 g/liter, i en mengde som er 3 ganger den støkiometriske mengde av kvikksølv, idet omrøring fort-settes i omtrent 1 time. Omrøringen ble deretter stanset for å muliggjøre at utfellingen fikk avsette seg. Etter en 3 timers henstand ble det overliggende klare vann trukket ut for å føres til filtreringstrinnet på aktivert trekull, hvorpå det resterende kvikksøiv-sulfidinnhold ble separert. a concentration of 5 g/liter, in an amount that is 3 times the stoichiometric amount of mercury, while stirring is continued for about 1 hour. Stirring was then stopped to allow the precipitate to settle. After a 3 hour standstill, the overlying clear water was drawn off to be fed to the activated charcoal filtration step, whereupon the remaining mercury sulphide content was separated.
Det kvikksølv-sulfid som var tilstede i avsetningsvannet i en mengde litt under 100 mikrogram/liter, ble etter filtrering The mercury sulphide which was present in the deposition water in an amount slightly below 100 micrograms/litre, was after filtration
nedsatt til verdier på fra 2-5 mikrogram/liter. reduced to values of 2-5 micrograms/litre.
I mellomtiden ble det alkaliske slam i avsetningstanken over-ført til en oppløsningsbeholder, hvor en del av det avløps-vann hvorfra kvikksølvet skulle fjernes er blitt tilsatt som sådant (dvs. ved pH omtrent 1,8) inntil oppnåelse av en pH-verdi mellom 2,2 og 2,5. I dette trinn ble omtrent 80% av slammet oppløst, idet det i form av et tungt uoppløst bunnfall In the meantime, the alkaline sludge in the settling tank was transferred to a solution tank, where part of the waste water from which the mercury was to be removed was added as such (ie at a pH of approximately 1.8) until a pH value between 2.2 and 2.5. In this step, approximately 80% of the sludge was dissolved, in the form of a heavy undissolved precipitate
bare ble etterlatt kvikksølvsulfidene og sulfidene av metall-ene i den første og annen gruppe i det periodiske system som eventuelt var rilstede i vannet. only the mercury sulphides and the sulphides of the metals in the first and second groups of the periodic table which were possibly present in the water were left behind.
Det resterende bunnfall ble passende samlet på et filter under vakuum, på en filterduk, uten at det var nødvendig med noe filterhjelpemiddel av dikalitt. The remaining precipitate was conveniently collected on a filter under vacuum, on a filter cloth, without the need for any dicalite filter aid.
Det vandige filtrat, som fremdeles inneholdt kvikksølvforbind-elser, ble resirkulert til natriumsulfidbehandlingen. The aqueous filtrate, which still contained mercury compounds, was recycled to the sodium sulphide treatment.
Bunnfallet, samles på filtret, som utgjorde omtrent 0,lg pr. liter vann som var blitt behandlet, hadde et innhold på omtrent 10% kvikksølv regnet som elementært metall. The precipitate is collected on the filter, which amounted to approximately 0.lg per liter of water that had been treated had a content of approximately 10% mercury, considered an elemental metal.
Forsøk i industriell målestokk er blitt gjennomført ved å følge samme trinnrekkefølge som i laboratoriet. Experiments on an industrial scale have been carried out by following the same sequence of steps as in the laboratory.
Det ble anvendt bare metalliske materialer i stedet for glassapparatur i stor størrelse. Only metallic materials were used instead of large-sized glassware.
Dimensjonene av det industrielle anlegg var reaktor 5 (beholder hvori væsken gjøres alkalisk) omtrent 300 m 3, flokkuleringsbeholder 6 omtrent 120 m 3, aktivert trekullfilter 8 omtrent 3 m 3 og alkalisk slam-oppløser 11 endelig 3m 3. The dimensions of the industrial plant were reactor 5 (container in which the liquid is made alkaline) approximately 300 m 3 , flocculation vessel 6 approximately 120 m 3 , activated charcoal filter 8 approximately 3 m 3 and alkaline sludge dissolver 11 finally 3 m 3 .
Også ved den industrille gjennomføring ble den nøytraliserende kalkmelk tilført ved hjelp av en måleinnretning inntil det ble oppnådd pH 8-9. Oppløsningen som var gjort alkalisk ble ført til flokkuleringsinnretningen hvortil det også ble til-ført natriumsulfid (i en mengde 3 ganger den støkiometriske mengde som kreves for utfelling av kvikksølvsulfid)for også å utfelle andre eventuelt tilstedeværende metaller, og det ikke-ioniske flokkuleringsmiddel ble tilsatt tidligere. Also in the industrial implementation, the neutralizing milk of lime was added using a measuring device until pH 8-9 was achieved. The solution which had been made alkaline was fed to the flocculation device to which sodium sulphide (in an amount 3 times the stoichiometric amount required for precipitation of mercuric sulphide) was also added to also precipitate any other metals that may be present, and the non-ionic flocculant was added previously.
Det er påvist at forbruket av flokkuleringsmiddel ved industrielle gjennomføring var bare halvdelen av forbruket funnet for gjennomføringen i laboratoriet: It has been shown that the consumption of flocculant in industrial implementation was only half of the consumption found for implementation in the laboratory:
Det mulige restoverskudd av natriumsulfid adsorberes ved The possible residual excess of sodium sulphide is adsorbed by
hjelp av det aktiverte trekullfilter. using the activated charcoal filter.
Vannet som kom ut fra flokkulerings- avsetningsbeholderen The water that came out of the flocculation settling tank
hadde et kvikksølvinnold mellom 50 og 200 mikrogram/liter. had a mercury level between 50 and 200 micrograms/litre.
Etter adsorpsjon på det aktiverte trekullfilter var den gjennomsnittlige konsentrasjon av kvikksølv i det utgående vann redusert til verdier på mellom 2 og 5 mikrogram pr. After adsorption on the activated charcoal filter, the average concentration of mercury in the outgoing water was reduced to values of between 2 and 5 micrograms per
liter. litres.
For å forhindre at enkelte flytende flokkulerte substanser To prevent certain liquid flocculated substances
skal tilstoppe det aktiverte trekullfilter, er et silika- should clog the activated charcoal filter, is a silica
filter anordnet på oppstrømssiden av dette. filter arranged on the upstream side of this.
Detslam som føres til oppløsningsinnretningen b] ir således behandlet med det vann hvorfra kvikksølvet skal fjernes, The sludge that is brought to the dissolution device is thus treated with the water from which the mercury is to be removed,
i in
Forholdet mellom surt vann og alkalisk slam er en funksjon av The ratio of acidic water to alkaline sludge is a function of
pH i vannet og konsentrasjonen av faststoffer oppslemmet i slammet og utgjør fra et minimum på 10 til et maksimum på 20. The pH of the water and the concentration of solids suspended in the sludge range from a minimum of 10 to a maximum of 20.
Etter hvert oppløsningstrinn får det surgjorte slam avsette After each dissolution step, the acidified sludge is allowed to settle
seg slik at det kan fjernes fra vannet ved avsugning. itself so that it can be removed from the water by suction.
Vannet resirkuleres til reaksjonsbeholderen. Det sure slam The water is recycled to the reaction vessel. The acidic sludge
fra oppløsningsbeholderen sendes til filtreringstrinnet i en filterpresse, slik at det oppnås en kompakt filterkako, som lett kan fjernes fra filterduken. from the solution container is sent to the filtration step in a filter press, so that a compact filter cake is obtained, which can be easily removed from the filter cloth.
Forsøk med fjernelse av kvikksølv har også for sammenligning vært foretatt med det samme avløpsvann,men uten behandling av det alkaliske slam med det vann hvorfra kvikksølvet skal fjernes. Experiments with the removal of mercury have also been carried out for comparison with the same waste water, but without treatment of the alkaline sludge with the water from which the mercury is to be removed.
Den mest påfallende forskjell var nødvendigheten av å The most striking difference was the necessity to
tømme avsetningstanken daglig og filtrere det alkaliske slam når dette oppnådde et for stort volum, mens i tilfellet med forsøkene med oppløsningstrinnet var det tilstrekkelig om enn ikke strengt nødvendig,å gjennomføre filtreringen hver uke. emptying the settling tank daily and filtering the alkaline sludge when this reached too large a volume, while in the case of the experiments with the dissolution stage it was sufficient, if not strictly necessary, to carry out the filtration every week.
Regenereringen av det aktiverte trekullfilter ble gjennom-ført in situ etter mer enn 45 døgns forsøk ved utvasking med en 3% oppløsning av saltsyre supplert med en korrosjons-inhibitor. The regeneration of the activated charcoal filter was carried out in situ after more than 45 days of testing by washing out with a 3% solution of hydrochloric acid supplemented with a corrosion inhibitor.
I de etterfølgende tabeller er data samlet vedrørende et antall tester gjort i samsvar med den i det foregående be-skrevne gjennomføring og for sammenligning er også tester foretatt uten slambehandling medtatt i tabellen. Verdiene for kvikksølvet inneholdt i det vann som skal behandles og det vann som kommer ut fra det aktiverte trekullfilter er gjengitt i 2 tilfeller, såvel som mengdene av slam ved utløpet for de to tilfeller, med respektive kvikksølvinnhold og andre data. In the subsequent tables, data is collected regarding a number of tests carried out in accordance with the previously described implementation and for comparison tests carried out without sludge treatment are also included in the table. The values for the mercury contained in the water to be treated and the water coming out of the activated charcoal filter are reproduced in 2 cases, as well as the amounts of sludge at the outlet for the two cases, with respective mercury content and other data.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
---|---|
NO814193L NO814193L (en) | 1982-06-14 |
NO154010B true NO154010B (en) | 1986-03-24 |
NO154010C NO154010C (en) | 1986-07-02 |
Family
ID=11219786
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO814193A NO154010C (en) | 1980-12-11 | 1981-12-09 | PROCEDURE FOR AA REMOVAL MERCURY OIL FROM SOURCE 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) | ES8300646A1 (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) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996020894A1 (en) * | 1994-12-30 | 1996-07-11 | Kemira Chemicals Oy | Method for treating waste water sludge |
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EP0324454B2 (en) * | 1988-01-14 | 2000-08-30 | Siemens Aktiengesellschaft | Process and apparatus for cleaning smoke |
WO1989009192A1 (en) * | 1988-03-31 | 1989-10-05 | Commonwealth Scientific And Industrial Research Or | Hydrometallurgical effluent treatment |
AU617166B2 (en) * | 1988-03-31 | 1991-11-21 | Commonwealth Scientific And Industrial Research Organisation | Hydrometallurgical effluent treatment |
DE4102972A1 (en) * | 1991-02-01 | 1992-08-13 | Ubib Unternehmensberatungs Gmb | METHOD AND DEVICE FOR RECYCLING LAMINATED LAMPS |
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 |
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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 GB GB8136195A patent/GB2089335B/en not_active Expired
- 1981-12-01 DE DE3147549A patent/DE3147549C2/en not_active Expired
- 1981-12-09 NO NO814193A patent/NO154010C/en unknown
- 1981-12-09 DK DK545381A patent/DK151375C/en active
- 1981-12-09 FR FR8123054A patent/FR2496083A1/en active Granted
- 1981-12-10 SE SE8107419A patent/SE444807B/en not_active IP Right Cessation
- 1981-12-10 BE BE0/206799A patent/BE891432A/en not_active IP Right Cessation
- 1981-12-10 ES ES508225A patent/ES8300646A1/en not_active Expired
- 1981-12-11 NL NL8105594A patent/NL8105594A/en not_active Application Discontinuation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996020894A1 (en) * | 1994-12-30 | 1996-07-11 | Kemira Chemicals Oy | Method for treating waste water sludge |
Also Published As
Publication number | Publication date |
---|---|
NO154010C (en) | 1986-07-02 |
DK151375B (en) | 1987-11-30 |
DE3147549C2 (en) | 1983-10-20 |
DK545381A (en) | 1982-06-12 |
DK151375C (en) | 1988-05-16 |
FR2496083A1 (en) | 1982-06-18 |
NL8105594A (en) | 1982-07-01 |
SE444807B (en) | 1986-05-12 |
FR2496083B1 (en) | 1984-12-28 |
BE891432A (en) | 1982-06-10 |
CH652707A5 (en) | 1985-11-29 |
DE3147549A1 (en) | 1982-06-24 |
IT1134671B (en) | 1986-08-13 |
NO814193L (en) | 1982-06-14 |
ES508225A0 (en) | 1982-11-01 |
GB2089335A (en) | 1982-06-23 |
IT8026563A0 (en) | 1980-12-11 |
GB2089335B (en) | 1983-06-22 |
ES8300646A1 (en) | 1982-11-01 |
SE8107419L (en) | 1982-06-12 |
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