V.

CONTROLUL POLUARII APEI SI AERULUI

Control END OF PIPE (la captul conductei) presupune intervenia la sfaritul procesului; Exista strategii de control care abordeaz proiectarea procesului, alegerea tehnologiilor optime, alte metode manageriale. I. APE PROCESE GENERATOARE DE POLUARE A APELOR Ape uzate provenite direct din procesele principale ape uzate provenite direct din operaii ale procesului. washing water from purification of products vapour condensates quench water (ape de clire) waste water from exhaust air (aerul evacuat) / flue gas clean-up (purificarea gazelor evacuate) waste water from equipment cleaning (curarea, splarea echipamentelor) waste water from vacuum generation. (de la producerea vidului) Tributary waste water (ape uzate din procese secundare) bleed (ape purjate - deversate, ) from boiler feed water systems (de la sistemele utilizate pentru alimentarea cu ap) - (probably containing corrosion inhibitors, biocides substane chimice cu efecte asupra microorganismelor, scale depuneri solide) blowdown (deversri) from cooling cycles back-washing of filters laboratory and pilot-scale plants (staii pilot) workshops (ateliere) sanitation waste water collection (salubrizarea apelor uzate colectate) collection of rainwater from contaminated areas landfill leachates,(levigate, scurgeri) might show toxic effects. Alternatively, synergetic effects of different individual streams, PRINCIPALII POLUANI REZULTAI DIN PROCESELE DE PRODUCIE Apele uzate sunt caracterizate prin: Concentraia sau ncrcarea cu substane poluante necombinate, ca: metale grele ((Pb2+, Cd2+, Cr3+ , Cr6+, Mn, .a), , substane anorganice (P,CN cianuri, fenoli, clor, detergeni, substane extractibile), + 3 uleiuri, ioni ( NH 4 , NO3 , PO4 ,Sulfuri si hidrogen sulfurat (S2-), Sulfiti (SO32-), Sulfati(SO42-), , Azot amoniacal (NH4+), etc. Efectul sau potenialul de pericol exprimat prin parametric sumativi ca TSS (total suspensii solide), BOD (consum biochimic de oxigen), COD (consum chimic de oxigen), AOX/EOX (Halogenuri organice adsorbabile/Halogenuri organice extractibile), VOX (Halogenuri organice volatile), pH, temperatur, conductivitate. Efectul asupra organismelor al apelor uzate, exprimat prin toxicitate, septicitate, mutagenitate Tabel 1-Unele substane prezente n principalele ape uzate industriale Prezente n apele uzate de la: Spltorii de rufe i mbrcminte, fabrici de hrtie, nlbire textile Fabricarea cocsului i benzinei, fabricarea substanelor chimice Scrubere pentru gaze, gravare n sticl, uzine de energie atomic Fabricarea benzinei, acoperiri metalice, curirea metalelor Vopsirea textilelor, tbcrii, fabricarea benzinei, fabricarea mtsii artificiale tip vscoz

Substane Clor liber Amoniac Fluoruri Cianuri Sulfuri

Acizi Alcalii Crom Plumb Nichel Cadmiu Zinc Cupru Arsen Zaharuri Amidon Grsimi. Uleiuri Fenoli Formaldehide Acid acetic Acid citric Fluoruri Hidrocarburi Ap oxigenat Mercaptani Acizi minerali Nichel Nitroderivai Acizi organici Argint Acid tanic Acid tartanic

Fabricarea substanelor chimice, mine, fabricarea DDT, berii, textilelor, fabricarea de baterii, soluii de fier i cupru Curirea lnii, mercerizarea bumbacului, spltorii de rufe i mbrcminte, fierberea bumbacului i a paielor Acoperiri metalice, tbcirea pieilor cu crom, eloxarea aluminiului Fabricarea bateriilor, fabricarea culorilor, fabricarea benzinei, mine de plumb Acoperiri metalice Acoperiri metalice Galvanizare, acoperiri cu zinc, fabricarea mtsii artificiale tip vscoz, prelucrarea cauciucului Acoperiri metalice de cupru, soluii de cupru, fabricarea mtsii artificiale Prepararea soluiilor de deparazitare Prelucrarea laptelui, fabricarea berii, fabrici de glucoz i zahr din sfecla de zahr, fabrici de ciocolat sau de dulciuri Prelucrarea unor alimente, industria textil, fabricarea tapetului Curirea lnii, spltorii, industria de textile, rafinrii de iei, lucrri inginereti Fabricarea de benzin i cocs, fabricarea rinilor sintetice, industria de textile, tbcrii, distilerii de gudroane, fabrici chimice, soluii pentru dezinfectare, fabricarea coloranilor Fabricarea de rini sintetice, fabricarea penicilinei i medicamentelor Fabricarea mtsii artificiale, fabricarea conservelor Buturi nealcoolice i prelucrarea citricelor Fabricare de benzin i cocs, fabricare de substane chimice, fabrici de substane fertilizatoare, fabrici de ceramic, fabricarea de tranzistori, gravarea sticlei Fabrici petrochimice i de cauciuc nlbirea textilelor, ncercarea motoarelor de rachet Rafinrii de iei, fabrici de pulp de lemn Fabricarea substanelor chimice, mine, soluii de fier i cupru, fabricarea DDT, fabricarea berii, textilelor, bateriilor Acoperiri metalice Fabrici de produse chimice i explozivi Distilerii i procese de fermentaie Acoperiri metalice, fotografie Tbcrii, fabrici de cherestea Colorarea vinului, pieilor, fabricarea de substane chimice

METODE I TEHNICI DE TRATARE I CONTROL The first treatment step for waste water and rainwater and often also the final step is the separation of suspended solids and immiscible liquids (with regard to water) from the main water stream. Separation or clarification techniques are: Gravity Separation (Grit (pietri) Separation, Sedimentation, Oil-Water Separation) Air Flotation Filtration (Filtration, Membrane Filtration). As a final step they remove solids formed during a preceding treatment operation or process, or remove oil before further biological treatment. They often follow treatment techniques applied to soluble pollutants, when these are transferred into solids. Solid-free waste water can either be segregated into a biodegradable and a non-biodegradable part, or the contaminants responsible for the non-biodegradability may be separated before further treatment. The treatment techniques for the non-biodegradable waste water part are based on physical and/or chemical operations, such as:

Precipitation / sedimentation / filtration Crystallisation chemical reactions (Chemical oxidation , Wet air oxidation, Supercritical water oxidation Chemical reduction and Chemical hydrolysis) Membrane filtration (Nanofiltration and Reverse osmosis) Adsorption Ion exchange Extraction Distillation Evaporation Stripping (stripare, barbotare) Incineration After adequate treatment, the waste water stream can either be discharged into a receiving water body, into a subsequent central biological WWTP or a municipal WWTP (Waste Water Treatment Plant staie de epurare). Biodegradable waste water or the remaining waste water part after elimination of the cause of the non-biodegradability are based on biological processes, such as: anaerobic digestion (Anaerobic contact process (ACP), UASB (Upflow Anaerobic Sludge Blanket reactor or process reactor cu strat de nmol cu flux ascendent) process, Fixed-bed process, Expanded-bed process and Biological removal of sulphur compounds and heavy metals) aerobic digestion, (Complete-mix activated sludge process, Membrane bioreactor process, Trickling - picurare filter process, Expanded-bed Process, Biofilter fixed-bed process) Nitrification / denitrification Many waste water treatment techniques require or optionally use treatment aids, which in most cases are chemicals, or the treatment media / equipment need regeneration, which can cause the release of chemicals. These aids (auxiliare) or process steps might generate, generally depending on local conditions, a pollution that needs to be taken into account when considering the use of a treatment technique. Thus, an assessment of treatment aids and chemicals released from regeneration facilities and their fate (evoluia lor) during the whole process might be necessary in specific situations. Almost all waste water treatment techniques have one thing in common: the production of solids during the process, which enables the pollutant to be separated from the aqueous medium, such as excess activated sludge or filtered or settled residue from filtration or sedimentation operations. If sludge is not recycled, it needs to be disposed of i.e. external treatment and disposal or treated on the site. Sludge treatment techniques are e.g.: Thickening (ngroarea) Dewatering (uscare) Stabilisation Conditioning Thermal sludge reduction (reducere termic a nmolului). Landfilling of sludge on site. SCWO oxidare cu ap supracritic MF/UF micro/ultra filtrare NF/RO nanofiltrare/osmoz invers SCWO oxidare cu ap supracritic trickling percolare= separare prin scurgere i dizolvare

Ape uzate industriale: origine, caracteristici i mod de epurare Ape uzate Originea principiilor eflueni Mod de epurare Caracteristici principale industriale provenite de la: 1 2 3 4 INDUSTRIA ALIMENTAR I A MEDICAMENTELOR Conserve, diferite Pregt.,selec., stoarcerea i Cantiti mari de suspensii, Grtare, epurare n lagune, decolorarea fructelor i substane coloidale i irigaii sau infiltraii n sol vegetalelor dizolvate

Produse din lapte Diluarea, separarea, prepararea Cantiti mari de substane untului i ndeprtarea zerului organice, ndeosebi proteine, grsimi i lactoz Fabrici de bere i Macerarea i presarea Cantiti mari de substane distilerii de grunelor, reziduurilor de la organice solide, dizolvate, buturi alcoolice distilarea alcoolului, Coninnd azot i amidon condensatul de la rafinarea fermentat sau produse ale evaporatului acestuia Carne i produse din psri de curte Grajduri, cotee, abatoare de animale, topirea grsimilor i oaselor, reziduurilor din condensate, grsimi i ape de splare, conservarea psrilor de curte Transportul sfeclei, supernatant de la nmolul de la tratarea cu var, condens dup evaporare, extragerea zahrului Micelium, filtratul epuizat, splare Cantiti mari de substane organice dizolvate i n suspensie, snge, diferite proteine i grsimi

Preparare, epurare biolog. conven. (bazine cu nmol activ sau filtre biologice) Recuperarea, concentrarea prin evaporare i centrifugare, filtre biologice; hran la animale Grtare, flotaie, decantare filtre biologice

Zahr din sfecl de zahr

Cantiti mari de substane organice dizolvate i n suspensie, coninnd zahr i proteine Produse Cantitate mare de substane farmaceutice organice n suspensie i dizolvate, incluznd vitamine Drojdie Filtrarea drojdiei (reziduu) Cantiti mari de solide, n special organice i CBO Murturi Pregtirea produselor (ap de pH variabil, cantiti mari de var, ap srat, alaun, sirop, substane n suspensie, semine i buci de castravei) substane organice, culoare Cafea Pregtire (pulp i boabe de CBO mare i cantiti medii de cafea) solide n suspensie Pete Centrifugare (deeuri), preparare CBO foarte mare, suspensii pete, ape uzate de la solide organice i miros evaporare ,.a. Splarea sticlelor, pardoselilor i pH mare, substane solide n Buturi echipam., drenarea rezervoarelor suspensie i CBO mediu nealcoolice de sirop Orez Inmuierea, prepararea i splarea CBO mare, substane solide, orezului n suspensie INDUSTRIA TEXTIL-PIELRIE Textile Pregtirea fibrelor, fabricarea Ape alcaline, colorate, cu materialelor CBO i temperatur mari, cantiti mari de substane solide n suspensie Produse de ndeprtarea prului, nmuierea, Cantiti mari de solide totale, pielrie pregtirea pentru introducerea n duritate mare, sare (NaCl), bi a pieilor sulfii, crom, pH 7, var preparat i CBO mediu Spltorii de rufe Splarea rufelor i mbrcmintei Turbiditate mare, alcalinitate, i mbrcminte subst. organice solide. INDUSTRIA CHIMIC Acizi Procesul tehnologic (ape uzate i pH mic, coninut redus de acizi diluai) substane organice

Refolosirea apelor uzate, coagularea i epurarea n lagune Evaporare i uscare, hran pentru animale. Fermentare anaerob, filtre biologice Reinere avansat a deeurilor n secie, grtare, egalizare. Grtare, decantare i filtre biologice Evaporarea n ntregime a apelor, resturi de pete n mare. Grtare, apoi descrcare n canalizarea oreneasc. Coagulare cu var, fermentare anaerob Neutralizare, precipitare chimic, epurare biologic convenional Egalizare, sedimentare i tratare biologic Grtare, precipitare chimic, flotaie i adsorbie Neutralizare, ardere cnd coninutul de substane

Detergeni Amidon din porumb

Splarea i purificarea spunurilor i detergenilor Evaporare (condensul), splare final (sirop), mbuteliere (ape uzate) Splarea TNT i a fulmicotonului pentru purificare, splarea i pregtirea ncrcturii

CBO i spunuri saponificate mari

CBO i substane organice dizolvate mari; n princip. Amidon i substane anexe Explozivi TNT, culoare, ape cu caracter acid, miros, coninut de acizi organici i alcool de la pulbere i bumbac, metal, uleiuri i spun Insecticide Splarea i purificarea produselor Mari cantiti de substane (2,4D i DDT) organice, structuri benzenice nchise, toxice pentru bacterii i peti, ape cu caracter acid Splarea, trecerea prin grtare i Argile, noroi i uleiuri, pH Fosfai i fosfor flotarea rocii, condens (rezultat alcalin, substane solide n din staia de reducere a suspensie, fosfor, siliciu i fosfatului) fluoruri Formaldehide Fabricarea enzimelor sintetice CBO normal i HCHO n (reziduuri), vopsirea fibrelor cant. mari (toxice pentru sintetice bacterii ) INDUSTRIA DE PRELUCRARE A MATERIALELOR Hrtie Pregtirea, rafinarea, splarea pH mare sau mic; culoare; fibrelor, trecerea prin grtare a substane solide n suspensie, pulpei de hrtie coloidale i dizolvate n cantitate mare Produse fotografice Oel Developare i fixare (soluii uzate) Pregtirea crbunelui, splarea gazelor de la furnale i de la finisarea oelului Striparea oxizilor, splarea i acoperirea metalelor

organice justific procesul. Flotaie i separarea grsimilor, precipitare cu CaCl2 Egalizare, tratare biologic convenional Flotaie, precipitare chimic, epurare biologic convenional, aerare, clorare, neutralizare Diluare, nmagazinare, absorbie cu crbune activ, clorare alcalin. Epurare n lagune, epurare mecanic. Coagulare i decantarea apelor rafinate Filtre biologice, adsorbie pe crbune activ.

Decantare, epurare n lagune, epurare biologic, aerare, recuper. substanelor pierdute n proces. Ape cu caracter alcalin, conin Recuperarea Ag, apoi diferii ageni de reducere evacuarea apelor uzate n organici i anorganici canaliz. or. pH mic, acizi, cianuri, fenol, minereu, cocs, piatr de var, alcalii, uleiuri, substane n suspensie fine Ape cu caracter acid, toxice, ndeosebi substane minerale Neutralizare, recuperare , reutilizare, coagulare chimic

Acoperiri metalice

Eliminarea cianurilor, reducerea i precip. cromului, precipitarea cu var a altor metale Produse din font ndeprtarea nisipului folosit prin Cantitate mare de subst. solide Grtare, uscarea nisipului evacuare hidraulic n suspensie, n special nisip; recuperat puin argil i crbune iei Din procesele tehnologice (noroi Cantiti mari de sruri din Recuperare, injecia n sol de foraj, sare, iei i gaze n iei, CBO mare, miros, fenoli a srurilor; acidificarea i cantiti mici, nmoluri acide i i compui cu sulf de la arderea nmolurilor diferite uleiuri de la rafinare) rafinrii alcaline Cauciuc Splarea latexului, coagularea CBO mare, miros, subst. Aerare, clorare, sulfonare, cauciucului, ndeprtarea solide n suspensie n cantiti epurare biologic impuritilor din cauciuc mari, pH variabil, cloruri n

cantiti mari Sticl Silozuri navale Polizarea i splarea sticlei Culoare roie, substane solide n suspensie nesedimentabile, ape cu caracter alcalin Splarea ncperilor, recuperarea CBO mare, ape cu caracter solvenilor i recuperarea apei acid din iei Precipitarea clorurii de calciu Recuperarea subst. pierdute n proces, egalizare, recirculare i refolosire, filtre biologice

INDUSTRIA ENERGETIC Centrale cu abur Rcire, drenare ape uzate, evacuarea boilerelor Prelucrarea crbunelui Curirea i clasificarea crbunilor, contactul straturilor de sulf cu apa

Ape calde, volum mare, substane solide dizolvate i substane anorganice n cantiti mari Cantiti importante de substane solide n suspensie; pH mic, H2SO4 mare i FeSO4

Rcirea prin aerare, depozitarea cenuii, neutralizarea excesului de acizi din apele uzate Decantarea, flotarea spumei i nmagazinarea sterilului

II. AER
PROCESE GENERATOARE DE POLUARE A AERULUI Waste gas streams can be divided into ducted (dirijate) and non-ducted (diffuse, fugitive) emissions. Only ducted emissions can be treated. As far as diffuse and fugitive emissions are concerned the objective of waste gas management is their prevention and/or minimisation (e.g. by capturing them in a ducted system). Waste gas and exhaust air emissions in the chemical industry are: ducted emissions, such as: - process emissions released through a vent pipe (conduct de ventilaie) by the process equipment and inherent to the running of the plant - flue gases from energy-providing units, such as process furnaces, steam boilers, combined heat and power units, gas turbines, gas engines - waste gases from emission control equipment, such as filters, incinerators or adsorbers, likely (presupuse) to contain unabated (ne-ndeprtai) pollutants or pollutants generated in the abatement system - tail gases (gaze reziduale) from reaction vessels and condensers - waste gases from catalyst regeneration - waste gases from solvent regeneration - waste gases from vents (orificii) from storage and handling (transfers, loading and unloading) of products, raw materials and intermediates - waste gases from purge vents (orificii de evacuare - purje) or pre-heating equipment, which are used only on start-up or shutdown operations - discharges from safety relief devices dispozitive de reducere (e.g. safety vents - supape, safety valves) - exhaust from general ventilation system - exhaust from vents from captured diffuse and/or fugitive sources, e.g. diffuse sources installed within an enclosure (instalate ntr-o ncpere)or building. diffuse emissions, arising (provenite) from point, linear, surface or volume sources under normal operating circumstances: - process emissions from the process equipment and inherent to the running of the plant, released from a large surface or through openings prin deschideri, etc.

- non-ducted emissions (e.g. working losses and breathing (prin respiraie) losses, when not captured and ducted) from storage equipment and during handling operations (e.g. filling of drums, trucks or containers) - non-routine emissions, resulting from operations other than the routine processing of the facility (a instalaiei), including emissions during start-up or shutdown, and during maintenance - emissions from flares - secondary emissions, resulting from the handling or disposal of waste (e.g. volatile material from sewers (canalizri), waste water handling (de operare manipulare a instalaiilor) facilities or cooling water). fugitive emissions, such as: equipment leaks (de scurgere) from pump and compressor seals (sifoane), valves, flanges (flane), connectors and other piping items (alte elemente de tubulatur), or other equipment items, such as drain or vent plugs or seals (cum ar fi dopurile de scurgere sau de aerisire sau garnituri). PRINCIPALII POLUANI REZULTAI DIN PROCESELE DE PRODUCIE The main air pollutants from industrial processes and energy supply are: carbon dioxide sulphur oxides (SO2, SO3) and other sulphur compounds (H2S, CS2, COS) nitrogen oxides (NOx, N2O) and other nitrogen compounds (NH3, HCN) halogens and their compounds (Cl2, Br2, HF, HCl, HBr) incomplete combustion compounds, such as CO and C xHy volatile organic compounds (VOC) and organosilicon compounds, which might encompass (conine) compounds with carcinogenic potential particulate matter (such as dust, soot, alkali, heavy metals) with possible carcinogenic properties.
THE SOURCES OF WASTE GASES TO BE TREATED ARE:

normal temperature processes, such as production, handling or work-up processes, with the main contaminants: - volatile organic compounds, such as solvents - inorganic compounds, such as hydrogen halides, hydrogen sulphide, ammonia, carbon monoxide - particulates in the form of dust (dust can include heavy metals) incineration processes, with main contaminants: - particulates in the form of ashes and dust, containing soot (funingine), metal oxides - flue gases (produse gazoase de ardere) such as carbon monoxide, hydrogen halides, sulphur-oxygen compounds, (SOx), nitrogen-oxygen compounds (NOx). Arising (care rezult) waste gases are treated by techniques where: the waste gas content is recovered (recuperat) and either (fiecare component) recycled to the original process or used in another process as raw product or energy carrier or the contaminants are abated (ndeprtai). Compounds, which are normally economically feasible to recover (a cror recuperare este posibil economic), include: VOC, recovered from solvent vapours or vapours of low-boiling (cu punct de fierbere sczut) products VOC used as energy carrier (folosii ca purttori de energie) in incinerators or boilers hydrogen chloride (clorur de hidrogen), transferred into hydrochloric acid ammonia to recycle into the production process sulphur dioxide, transferred into sulphuric acid, sulphur or gypsum dust containing higher amounts of solid raw products or end products

METODE, TEHNICI I SISTEME DE TRATARE I CONTROL The treatment techniques are classified as: recovery techniques for VOC and inorganic compounds: - membrane separation - condensation - adsorption - wet scrubbing abatement techniques for VOC and inorganic compounds: - biofiltration - bioscrubbing bioepurare (bioscrubbing combines wet gas scrubbing (absorption and biodegradation, the scrubbing water containing a population of microbes suitable to oxidise the noxious gas components. The microbes are suspended in water). - biotrickling (biotrickling works with similar conditions to bioscrubbing. In contrast to bioscrubbing, the microbes are fixed on supporting elements; trickling percolare= separare prin scurgere i dizolvare) - thermal oxidation - catalytic oxidation - flaring (incinerare) recovery and abatement techniques for particulates, using: - gravitational separator - settling chamber - cyclone - electrostatic precipitator - wet dust scrubber - fabric filter, including ceramic filter - catalytic filter - two stage dust filter - absolute filter (HEAP - filtru de particule de nalt eficien ) - high efficiency air filter (HEAF) - mist (cu pulverizare) filter for gaseous pollutants in combustion exhaust gases: - dry sorbent injection - semi-dry sorbent injection - wet sorbent injection - selective non-catalytic reduction of NOx (SNCR) - selective catalytic reduction of NO x (SCR).

10

11

Controlul puberilor n funcie de principalele caracteristici:

Controlul oxizilor de sulf - utilizarea combustibililor cu coninut redus de sulf - utilizare sorbeni (prin absorbie sau adsorbie) uscai sau umezi care folosesc prin injecie sau pulverizare substane alcaline calcar, var; Oxizi de sulf Acid sulfuros (sulfuric) Sruri (sulfai, sulfii) Controlul oxizilor de azot - controlul arderii pt. a reduce formarea oxizilor de azot (reducerea excesului de aer - amestec bogat, recirculareagazelor arse, ardere la temperaturi sub cele de formare a NOx) - reducerea selectiv i reducerea catalitic selectiv utiliznd amoniac sau uree (adesea dispuse n straturi sau paturi) care reduc oxizii de azot la azot molecular i ap Controlul COV - oxidarea (arderea) termic i catalitic adsorbia prin straturi sau paturi adsorbante cu medii poroase crbune active, zeoliti, polimeri - Condensare, refrigerare i criogenare - ndeprteaz vaporii organici prin condensarea lor pe suprafee reci. - Oxidarea biologic; Compuii organici volatili pot fi ndeprtai prin forarea absorbiei lor n lichid apos sau medii umede care conin microorganisme care consum compuii organici dizolvai sau absorbii. Toate tehnicile de control sunt aplicabile pentru concentraii de COV sub valoarea de 25% din L.E.L. (lower explosive limit). 12

Concentraia COV Mic (sub 500 ppm.) Mare (peste 500 ppm.)

Numr compui COV Maximum 3 Peste 3 Maximum 3 Peste3

Metode de control Adsorbie*, Oxidare termic, Oxidare catalitic, Oxidare biologic Oxidare termic, Oxidare catalitic, Adsorbie Adsorbie*, Condensare/Refrigerare*, Oxidare termic, Oxidare catalitic Oxidare termic, Oxidare catalitic

* cu posibilitate de recuperare a compuilor COV Controlul halogenilor- care au un caracter acid (conin HCl, HF) pe straturi sau prin injecie de absorbani i adsorbani cu caracter alcalin Controlul compuilor incomplet oxidai (Compui organici, monoxid de carbon) prin reglarea arderii, n sensul creterii excesului de aer, la temperaturi i umiditi optime de ardere (n sens invers fa de reducerea oxizilor de azot)

13