Emissions to water

However, flue-gases emitted by sulphur recovery units are typically highly concentrated, representing, at the site level, small volumetric contributions which are rarely measured and often estimated with rather significant uncertainty. As an alternative - which corresponds to Column (f) in Table 3.14 - these small volumetric contributions could be neglected. The equivalent concentration would then be calculated with the mass contributions from the four categories of sources mentioned above, but only divided into the volumetric contributions from:

• furnaces and boilers

• CHPs and gas turbines

• and FCC units.

With this option, data necessary for the calculation are available for a wider sample of 32 sites, of which 10 are non-FCC sites and 22 are FCC sites. The site equivalent concentrations obtained for the whole group of refineries are, on average, slightly higher than those obtained in the first case, due to their artificial ‘enrichment’ related to the decrease of the overall flue-gas volume.

The resulting discharge of the aforementioned substances depends on the ‘in-process’

preventive measures (knowledge of all streams, reduction at source, good housekeeping, reuse) and the presence and technical standards of waste water treatment facilities. The typical process water pollutants and/or waste water parameters relevant to the overall refining process and prior to any purification steps are as stated in Table 3.15.

Table 3.15: Representative concentrations of pollutants in typical refinery effluents before treatment

Source Oil H2S

(RSH)

NH3

(NH4+) Phenols

BOD COD TOC

CN

-(CNS^-) TSS Distillation Units

Hydrotreatment Visbreaker Catalytic Cracking Hydrocracking Lube oil Spent caustic Ballast water Utilities (Rain) Sanitary/Domestic

XX XX XX XX XX XX XX X - (X)

-

XX XX(X)

XX XXX XXX X XX

- - -

XX XX(X)

XX XXX XXX X

- - - X

X - XX XX - - XXX

X - -

XX X(X)

XX XX X XX XXX

X X X

- - X X - - X X - -

XX - X X - - X X - XX Key: X = <50 mg/l XX = 50 – 500 mg/l XXX = >500 mg/l

Source: [ 166, CONCAWE 1999 ]

Table 3.16 summarises the annual average range of the water effluents from European refineries. Most data were gathered in 2009 – 2010 by the Technical Working Group set up for the revision of this document, and relate to a sample of 44 sites, all equipped with a dedicated WWTP. These data reflect an annual period of continuous emissions between the years 2006 and 2008.

The details on the various treatment steps in operation at the refinery sites are shown in Section 4.24.

More detailed data on the main parameters used for characterising organic and nitrogen compounds are shown in Table 3.17 and Table 3.18. The actual range and distribution shape of annual average concentrations and their eventual correlation with related specific emissions are displayed in Figure 3.20 to Figure 3.25, respectively for parameters TOC, COD, BOD5, TSS and Total Nitrogen. These particular figures only concern data relating to refineries where aqueous effluents are treated in a single dedicated waste water treatment plant.

The amount of oil discharged is usually expressed in grams of Total Hydrocarbon Content (THC) per tonne of refinery throughput. According to CONCAWE, nearly 90 % of the European refineries meet the standard of the Oslo/Paris Commission of 3 grams THC/tonne of refinery throughput since the early 1990s.

Table 3.16: Typical refinery influent/effluent annual average composition and load

Parameter

Composition after pretreatment by API, CPI and SWS

Annual effluent composition

downstream WWTP Specific load

(g/t feedstock) No (²) Average Max. Min. – Max.

pH (pH unit) 7 10 6 – 9

Temperature (°C) 25 45 10 – 35

5th–95th Percentile

50th Percentile

5th–95th Percentile

50th Percentile

Concentration in mg/l

TOC 100 250 4 – 50 14 1 – 15 5.5 22

COD 300 – 500 1000 19 – 125 66 9 – 85 27.2 38

BOD5 80 – 150 300 2 – 30 10 0.5 – 25 4.4 31

HOI (³) 40 – 50 100 0.05 – 6.3 1.5 0.1 – 3 0.4 15

HOI (⁴) NA NA 0.3 – 5 1.2 0.03 - 10 0.6 11

TSS 20 – 60 200 4 – 35 15 1 – 30 6.3 37

AOX (¹) NA NA 0 – 6 0.2 0 – 0.5 0.06 14

Ammonium-N 12 – 15 30 0.3 – 15 2.7 0.1 – 10 1.2 19

Nitrites-N NA NA 0.03 – 1.5 0.2 0.05 – 0.7 0.1 13

Nitrates-N NA NA 0.4 – 12 1.7 0.2 – 3 1.4 15

Kjeldahl nitrogen 25 50 2 – 20 5.4 1 – 6 2.3 13

Total Nitrogen 25 50 3 – 22 8 1 – 20 4 38

Phosphate 5 20 0.1 – 1.5 0.3 0.05 - 1 0.13 7

Total Phosphorus NA NA 0.05 – 4 0.6 0.05 – 2 0.3 26

Anionic agents NA NA 0.2 – 0.3 0.25 0.1 – 0.2 0.15 2

Cyanide (¹) 0 – 3 5 0.003 – 0.1 0.015 0.001 – 0.03 0.004 16

Sulphide 5 10 0.005 – 0.2 0.05 0.002 – 0.25 0.025 16

Phenols 12 25 0.01 – 0.4 0.1 0.001 – 0.3 0.02 29

MTBE (¹) 0 – 3 15 0.003 – 0.1 0.02 0.001 – 0.03 0.005 3

Fluoride (¹) 0 – 30 60 0.2 – 3 0.8 0.3 – 2 0.6 7

Benzene NA 10 <0.001 – 0.1 0.001 <0.001 – 0.05 0.002 10

Toluene NA NA <0.001 – 0.6 0.003 <0.001 – 0.1 0.004 10

Ethybenzene NA NA <0.001 – 0.005 0.001 <0.001 – 0.007 0.004 9

Xylenes NA NA <0.001 – 0.2 0.001 <0.001 – 0.15 0.004 7

BTEX 5 10 <0.001 – 1 0.005 <0.001 – 0.2 0.01 10

PAH-16 0.1 0.5 <0.0001 – 0.01 0.0007 <0.0001 – 0.005 0.0003 11

Arsenic-As NA NA <0.001 – 0.02 0.003 <0.001 – 0.02 0.0007 21

Boron-B NA NA 0.2 – 0.6 0.4 NA NA 4

Cadmium-Cd NA NA <0.001 – 0.05 0.001 <0.0001 – 0.005 0.001 18

Chromium-Cr NA 100 <0.001 – 0.05 0.003 <0.0001 – 0.005 0.001 23

Chromium VI NA NA <0.001 – 0.02 0.002 <0.0001 – 0.002 0.001 7

Cobalt-Co NA NA <0.001 – 0.003 0.001 NA NA 3

Copper-Cu NA NA 0.01 – 0.1 0.05 <0.001 – 0.03 0.002 27

Iron-Fe NA NA 0.15 – 3 0.4 0.01 – 0.6 0.15 14

Mercury-Hg NA NA <0.0001–0.003 0.0002 <0.0001 – 0.002 0.0001 21

Manganese-Mn NA NA 0.02 – 0.5 0.08 0.001 – 1.8 0.04 9

Molybdenum-Mo NA NA 0.004 – 0.02 0.01 NA NA 4

Nickel-N NA NA 0.002 – 0.1 0.01 <0.001 – 0.03 0.006 22

Lead-Pb NA 10 <0.0001 – 0.01 0.001 <0.0001 – 0.02 0.005 25

Selenium-Se NA NA 0.003 – 0.08 0.04 NA NA 5

Stain-Sn NA NA <0.001 – 0.02 0.01 <0.0005 – 0.005 0.004 6

Vanadium-V NA NA 0.005 – 0.1 0.02 <0.001 – 0.01 0.003 10

Zinc-Zn NA NA 0.005 – 0.12 0.03 <0.001 – 0.1 0.015 29

Heavy metals (⁵) 1 2 0.05 – 1.0 0.2 0.02 – 2 0.1 -

(¹) Dependent on whether or not relevant units are part of the refinery.

(²) Number of available site yearly concentration values provided to the TWG.

(³) Hydrocarbon Oil Index measured according to method EN 9377-1.

(⁴) Hydrocarbon Oil Index measured according to method EN 9377-2:2000 (GC-FID).

(⁵) Sum of individual percentile data for the following metals: Cd, Cr, Cu, Hg, Mn, Ni, Pb, Se, Sn; V, Zn.

(-) Not appropriate.

Source: [TWG data collection questionnaires]

Table 3.17: Emissions of main organic pollutants and suspended solids from a sample of 48 European sites

Site label Total feed refined Dedicated WWTP TOC BOD5 COD TSS

kt yes=1 mg/l g/t kg/yr mg/l g/t kg/yr mg/l g/t kg/yr raw final kg/yr

38 8183 0 50.0 5.4 44000 60 6.5 53000 170 18.3 150000 49.0 43000

1 9096 0 10 7.4 67000 5 3.9 35510 28 20.3 184920

6 12400 0 21.5 266897

26 10193 0 14 7.8 79967 115 54.3 553019 71 62.8 350232

58 11430 0 6.9 78937 61.3 700976 157515

30 10490 0 102 16.9 176843 374 61.7 647501 72.8 125970

27 19151 0 15 115 200 25.0

31 12087 0 29.2 10.6 128406 127 76.9 377678

48 6900 0 94.6 652522

51 4400 0 138.4 608808

35 3624 1 20.4 1.3 4630 8 0.5 1774 74 4.6 16771 14.2 3211

56 6276 1 20.6 2.4 14919 4 0.4 2818 55 6.3 39701 56 8.6 6235

11 9350 1 13 2.2 20983 9.1 84684 7.3 11571

39 10098 1 9.0 2.5 25600 3 0.9 9000 33 9.3 94000 9 9.0 25600

40 5668 1 11.7 3.0 16900 8 2.1 11700 42 10.6 60000 24 4.2 6000

41 3942 1 4.3 16900 11.4 44900 10800

4 4900 1 2 0.7 3524 37 11.5 56397 6.5 9770

19 3359 1 31 4.4 14782 82 11.9 39936

17 728 1 24 3.0 2184 112 13.9 10115 29.7 2679

47 11871 1 4.0 1.0 11857 65 14.8 175 364 72 17.0 45043

15 4858 1 18.0 4.1 19959 10 2.2 10881 88 16.5 80365 25 20.0 20395

42 10916 1 22.0 5.6 61139 66 17.1 186463 36 10.0 29352

59 3513 1 9.27 1.5 5331 95.88 18.6 65333 22.6 13007

12 6412 1 12.8 5.5 35100 5 2.1 13329 44 18.8 120274 7.9 21569

50 4620 1 12.5 5.4 25162 27 11.6 53508 45 19.7 91085 17.2 34557

52 4990 1 18.1 7.6 38000 53 22.4 112000 4.8 10000

34 10462 1 1.3 0.5 5293 23.3 243508

28 14251 1 55 26.2 372765 100 6.4 43509

9 5727 1 2 3.2 18300 21 26.7 152838 8.5 61319

16 7153 1 15.2 5.6 40020 8 2.9 21031 73 27.6 197587 12.0 32967

46 9712 1 12.0 3.7 36397 98 29.5 286809 13.0 37792

36 5622 1 13 6.8 38002 59 31.4 176436 13.5 40716

7 3268 1 4 17.9 58390 8 31.4 102758 6.3 86301

10 8852 1 24 5.5 48444 136 31.7 280318 80 32.0 67095

22 8635 1 10.0 8.2 70985 18 14.2 122237 41 33.0 284850 19.9 138938

32 5886 1 46.8 14.9 87834 111 35.4 208325 178 22.4 42040

25 3613 1 48 35.9 129597 21.8 59375

57 5778 1 8 5.6 32318 53 36.3 209729 23.5 92272

37 7293 1 109 38.9 283706

5 2772 1 6 3.5 9800 90 49.8 138000 14.8 22 700

49 15000 1 32 10.7 160810 149 49.9 748772 19.0 95 481

13 5303 1 13 8.3 43989 76 50.1 265582 16.3 57 490

18 8272 1 13 15.3 126700 47 55.7 460640

14 16552 1 14 9.1 151450 95 56.2 930051 10.7 104707

29 3817 1 10.7 6.9 26213 20 13.0 49733 121 77.3 295211 22.2 54387

8 953 1 25 37.7 35939 80 110.7 105561 14.0 18637

33 4610 1 65.5 18.6 85800

53 1 16.0 21000 10 12000 40 48000 15.0 36000

54 10794 1 20.3 7.7 82706 47.0 199780

60 1 8.2 18253 2.53 5256 40.23 83353 10.3 21425

61 1 15.0 157701 15 162733 97 1028 23.3 246

No of

values 48 51 24 23 26 34 32 35 41 42 45 12 39.0 41

5th percentile (¹) 3.9 0.9 11528.8 2.4 0.8 3100 29.4 9.2 35263 15 5.7 5004 50th percentile (¹) 13.9 5.5 30656.5 11.3 4.3 20983 65.0 26.7 133799 56 14.0 34557 95th percentile (¹) 47.7 15.7 91327.4 29.7 17.2 157066 125.2 62.5 503860 147 30.6 114976 (¹) Only for sites with a dedicated WWTP.

Source: [TWG data collection questionnaires]

Table 3.18: Emissions of nitrogen compounds from a sample of 51 European sites

Site label WWTP Total feed Ammonium (NH4 - N)

Nitrites (NO2 - N)

Nitrates (NO3 - N)

Nitrogen Kjeldahl

Total nitrogen (as N) (¹) kt (²) mg/l g/t kg/yr mg/l g/t kg/yr mg/l g/t kg/yr mg/l g/t kg/yr (²) mg/l g/t kg/yr

1 0 9096 0.9 10.70

6 0 12400 6.51 80721

26 0 10193 12.52 127639 9.80 4.63 47170 27 17.15 174808

27 0 19151 0.60 1.60 11.00 13.00

30 0 10490 71.00 11.71 122856

31 0 12087 7.3 2.64 31950 16.80 4.67 56400

38 0 8183 12.0 1.34 11000 16.00 1.71 14000 24.00 2.58 21100

48 0 6900 54.93 378998

51 0 4400 21.02 92483

58 0 11430 17.62 201442

4 1 4900 0.34 1655 1.23 6030

5 1 2772 1.84 5100

7 1 3268 21 4.50 18.67 61017

8 1 953 0.20 0.34 320 1.40 1.95 1858 3.40 4.56 4343 4.90 6.84 6521

9 1 5727 3.57 4.58 26248

10 1 8852 30.00 6.99 61877

11 1 9350 0.98 9158

12 1 6412 5.40 2.28 14590

13 1 5303 23.18 15.62 82859

14 1 16552 8.10 4.80 79500

15 1 4858 11 6.19 0.60 7.00 13.00 21 17.00 4.11 19960

16 1 7153 0.58 0.73 1597 3.77 6.31 10192 11.20 4.08 29215

17 1 728 4.02 2930

18 1 8272 7 0.9 1.10 9096 0.09 0.11 910 0.60 0.71 5846 1.42 1.64 13563 19 1 3359 14.8 2.28 7669

22 1 8635 1.7 1.37 11838 0.05 0.04 349 2.40 1.91 16536 5.40 4.35 37601 25 1 3613 4.2 2.75 9945 0.08 0.06 220 0.34 0.24 854

28 1 14251 4 0. 0.41 5805 0.80 0.38 5438 9 2.20 1.09 15541

29 1 3817 0.00 1.70 4.30 6.60 3.27 12494

32 1 5886 16.8 5.36 31530 18.90 6.03 35472

33 1 4610 49.24 227000

34 1 10462 1.66 17371 2.60 27239 5.20

35 1 3624 2.7 0.17 615 2.39 8660

36 1 5622 15 2.7

37 1 7293 9.80 3.50 25508

39 1 10098 5 0.5 0.14 1400 8 1.60 0.45 4500

40 1 5668 2.5 0.58 3300 4.00 1.01 5700

41 1 3942 0.46 1800 400 1.24 4900 2.82 11100

42 1 10916 23 0.4 0.10 1037 43 19.50 5.04 55000

46 1 9712 4.2 1.25 12108

47 1 11871 19 5.00 0.98 11596

49 1 15000 0.12 0.07 1060 0.49 0.16 2467 16.70 5.59 83823 18.32 5.47 82064 50 1 4620 2.24 3.13 4402 5.95 11.80 12261 5.21 2.25 10385 13.42 5.51 25452

52 1 4990 32 2.7 6.00 2.00 10000

53 1 2 0.04 50 40 15.00 18000

54 1 10794 7.5 2.87 30991 9.10 3.51 37851

56 1 6276 4.00 0.45 2837

57 1 5778 5.59 32318 5.88 33955

59 1 3513 4.58 0.75 2635 0.51 0.08 291.7 20.51 3.36 11789 8.12 1.33 4666 27.96 4.80 16856

60 1 1.45 2995 0.12 238.5 5.44 11275 2.98 6171 8.13 16944

61 1 8.95 94475 0.88 9277 1.00 10508 13.04 624.5 13.87 146349

No 51 48 8 22 19 22 13 8 11 15 13 15 13 8 10 8 31 38 41

Average (³) 7579 12 4.71 1.64 14617 0.47 0.23 1733 4.60 2.37 17520 9.86 3.57 24281 23.5 12.84 8.19 56152 5th perc. (³) 2499 2 0.36 0.13 587 0.03 0.05 229 0.43 0.20 1456 3.19 1.08 2112 8.24 1.75 0.69 3872 50th perc. (³) 5753 9 2.70 1.10 6737 0.16 0.10 400 1.70 1.42 10192 5.40 2.28 9158 21.2 8.12 4.05 18000 95th perc. (³) 14363 29 15.00 5.40 35426 1.49 0.74 6840 12.40 3.00 20817 20.35 6.57 75045 42.1 22.26 17.30 108255 (¹): 0 = collective, 1 = dedicated. (²): intermediate concentration (in mg/l) after API, CPI and SWS. (³): only for dedicated WWTP.

Source: [TWG data collection questionnaires]

Figure 3.20: Distribution of COD emissions for a sample of 36 European refineries

Figure 3.21: Distribution of BOD5 emissions for a sample of 29 European refineries

Figure 3.22: Distribution of TOC emissions for a sample of 21 European refineries

0 20 40 60 80 100 120 140 160

0,0 20,0 40,0 60,0 80,0 100,0 120,0

COD (mg//l) COD (g/t)

0 5 10 15 20 25 30 35

0,0 5,0 10,0 15,0 20,0 25,0 30,0 35,0 40,0

BOD5 (mg/l) BOD5 (g/t)

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