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104 AZERBAIJAN CHEMICAL JOURNAL № 4 2023 ISSN 2522-1841 (Online)
ISSN 0005-2531 (Print)
UDC 5:54.504
DETERMINATION OF ECOTOXIC SUBSTANCES IN WASTEWATER FORMED IN THE PURIFICATION PROCESS OF PETROLEUM OILS WITH HYDROGEN BY
SPECTRAL METHODS
A.M.Huseynli, G.I.Bayramov
Baku State University atlashuseynli@yahoo.com
Received 10.11.2022
Accepted 03.03.2023
The article analyzes the determination of the amount of dissolved ecotoxicants in the sample taken from the industrial wastewater obtained during the process of hydrogen treatment of petroleum oils. During the hydrogenation process, different types of wastes are formed, depending on the nature of each compound contained in petroleum distillates. Every gas, liquid, solid waste formed during the process of hydrogen purification of petroleum distillates by the oil refining industry has a negative impact on the environment in various ways. One of the main directions of our scientific research is the ecological assessment of the environmental impact of wastewater formed in the process of hydrogen treatment of petroleum distillates.Based on the results obtained, the environmental impact of the wastewater was assessed. The amount of volatile ecotoxicants in the wastewater sample was determined by spectral methods and is shown in the table. We used gas chromatography-mass spectrometry method for the polycy-clic aromatic hydrocarbons; optical emission spectrometry method for metals; spectrometry method for phenols, dyes and fluorine; nephelometry method for turbidity; the gravimetry method for total suspended particles. Based on the results obtained, it is possible to assess the environmental impact of wastewater generated during the technological process at the hydrogen treatment plant. According to the results of the research, it can be noted that the industrial wastewater discharged from the oil refinery's facility № 501 has a content that will damage the ecosphere and biosphere, despite the fact that the discharge standards meet the permissible discharge limits.
Keywords: petroleum distillates, hydrogen purification, spectral method, ecotoxicants, effluents.
doi.org/10.32737/0005-2531-2023-4-104-m Introduction
The hydrogen treatment plant for petroleum distillates and other oil distillates at the Heydar Aliyev Oil Refinery is considered to be more environmentally and economically efficient than the old classical technological plants. As it is known, so far the complete reduction of emissions has not been achieved during the technological processes of oil refining in the developed countries of the world oil industry [1-3].
That is why conducting environmental research in various areas is one of the most important topics in the assessment of environmental impact of each of the many existing technological processes in the oil refining industry, as one of the main environmental safety requirements of the time [4, 5]. From this point of view, the main urpose of our research is to program an environmental assessment of the environmental impact of the process of hydrogen
purification of petroleum oils at the facility № 501 of the Heydar Aliyev Oil Refinery [6]. One of the industrial wastes generated during the technological process of this facility is waste-water. The amounts of ecotoxicant organic and inorganic substances in the water sample taken from the effluent of the plant's industrial waste-water were determined by the mass spectrum method in the laboratory.
Ecotoxicants in soluble form in industrial wastewater formed when using Autol 8 and Au-tol 15 oil distillates as raw materials in the hydrogen cleaning process mentioned by us were determined spectrally. As noted in the technical literature, the process of hydrogen purification of petroleum oils has great economic and environmental advantages. Thus, the process of preparation of petroleum distillates as a commodity has been carried out for many years by acid-base, contact methods. Even in the oil refining
industry of Azerbaijan, as in many countries, these classic processes are currently used in small quantities, which in turn creates environmental problems.In the process of refining oil and oil distillates by the above-mentioned classical methods, economically and ecologically effective, high-quality petroleum oils are produced, despite the fact that they create a very dangerous and harmful conditions [7-9].
In this case, fumes of sulfuric acid, sodium hydroxide and other ecotoxicants are go up into the atmosphere, along with harmful hydrocarbons of various compositions. At the same time, acidic waters containing aromatic hydrocarbons and other harmful substances containing polystyrene wastewater are discharged into water bodies without thorough cleaning. It is known that in the oil refining industry, as in other industries, it has not yet been possible to carry out completely waste-free technological processes [11-15].
From this point of view, various types of industrial wastes are formed during the plant of the purification processes with hydrogenation of petroleum oils of Heydar Aliyev Oil Refinery during the for the production of various brands of petroleum oils, as well as light oil distillates as commodities [16]. One of the main directions of our research is the initial assessment of the environmental impact of wastewater generated at the facility. The following analyzes were performed for this purpose.
Experimental part
Spectral analysis of volatile ecotoxicants in
water samples taken from wastewater formed during the hydrogenation of Autol 8 and Autol 15 oil distillates as catalysts as the main raw material was carried out in the above-mentioned facility.
We use gas chromatography-mass spectrometry method for the analysis of PAH (Poly-cyclic aromatic hydrocarbons); optical emission spectrometry method for metals; spectrometry method for phenols, dyes and fluorine; nephe-lometry method for turbidity; gravimetry method for common suspended particles. These methods are shown in the table below (Table 1).
The results obtained during laboratory measurements by taking water samples from the general wastewater outlet of the facility in accordance with the known methods are shown below (Table 2 and 3).
As can be seen from the results obtained from the tables, the reasons for the formation of all volatile organic and inorganic substances with all ecotoxicant properties in the water sample taken from the plant of the refinery can be explained as follows:
- Chemical transformations of hydrogen gas with Autol 8 and Autol 15 distillates due to the presence of sulfur, nitrogen, oxygen, phosphorus organic compounds, various mixtures of hydrocarbons and metal salts and catalysts, pressure and temperature up to 280-3100C resulting in volatile ecotoxicants.
- Although the individual quantities of the refinery are less than normal, as can be seen from the table, their total amount is very high and toxic.
Table 1. Methods of studying the com] position of industrial wastewater
Assigned indicator Method MDL MU
Blurring SM 2130 1 NTU 5%
Color SM 2120C 2.5 color (mg/l Pt) 10%
Common suspended solids EN 872; SM 2540D 2 mg/l 5%
Fluorides Spectroquant Fluoride Test 1.14598.0001, 1.14598.0002 (0.1-20 mg/l) 0.1 mg/l F 10%
Phenols (spectrophotometric method) SM 5530D 0.03 mg/l 10%
Aluminum (Al) ISO 11885, SM 3120B, EPA 6010D 0.02 mg/l 15%
Cobalt (Co) ISO 11885, SM 3120B, EPA 6010D 0.008 mg/l 15%
Molybdenum (Mo) ISO 11885, SM 3120B, EPA 6010D 0.005 mg/l 15%
Nickel (Ni) ISO 11885, SM 3120B, EPA 6010D 0.008 mg/l 15%
Polycyclic aromatic hydrocarbons EPA 3510C; EPA 3630C; EPA 8270D 0.01 mg/l 20%
MDL - Minimum setting limit MU - Possible error in measurement
Table 2. Results of analysis of industrial wastewater
Assigned indicator Amounts. mg/l
Polycyclic aromatic drocarbons (PAH)
Naphthalene 9.8
Acenaphthylene 0.06
Acenaphthene 0.06
Fluorene 0.17
Phenanthrene 0.27
Anthracene 0.18
Fluoranthene 0.23
Pyrene 0.36
Benzo (a) anthracene 0.34
Chrysene 0.53
Benzo (b + j + k) fluoranthene 0.30
Benzo (a) pyrene 0.18
Indeno (1,2,3-cd) pyrene 0.08
Benzo (ghi) perylene 0.09
Dibenzo (ah) anthracene 0.09
X 16 PAH 12.7
Table 3. Results of analysis of industrial wastewater
Naphthalene-9.8; Acenaphthylene 0.06; Acenaphthene 0.06; Fluorene 0.17; Phenan-threne 0.27; Anthracene 0.18; Fluoranthene 0.23; Pyrene 0.36; Benzo (a) anthracene 0.34; Chrysene 0.53; Benzo (b+j+k) fluoranthene 0.30; Benzo (a) pyrene 0.18; Indeno (1,2,3-cd) pyrene 0.08; Benzo (ghi) perylene 0.09; Diben-zo (ah) anthracene 0.09.
As can be seen from Table 3, the total amount of suspended solids and fluorides is above normal and their harm to human health is known to science.The content of dissolved eco-toxicants in the waste water sample of the plant depends mainly on the amount of sulfur, nitro-
gen, oxygen, metal, etc. compounds in the raw materials Autol 8 and Autol 15 distillates, as well as petroleum acids. The following are views of chromatograms of spectral analysis:
Thus, in short, the following explanations can be given about the technological process of hydrotreating of petroleum distillates and the reactions that take place during this process.
-The hydrotreating process is carried out in a hydrogen environment with the presence of alumocobaltmolibdenum and alumonicelmolibde-num catalysts at a temperature of 3 50-43 00C, 3070 atmospheres, 100-600 m3 of circulating hydrogen gas as raw material and 60-95% hydrogen.
-During this process occur reactions such as hydro-desulfurization, hydrocracking, hydrogenation of unsaturated hydrocarbons, isomeri-zation of paraffin and naphthenic hydrocarbons.
-During the hydrogenation process, different types of wastes are formed, depending on the nature of each compound contained in petroleum distillates. Phenols, ketones, alcohols in the resin formed in the technological process are easily reduced by hydrogen.
-The mixture of these resins is saturated with hydrogen and broken down to form hydrocarbons, hydrogen sulfide, ammonia and the above-mentioned volatile compounds with eco-toxicant properties. Wastewater containing a mixture of dissolved ecotoxicants is separated from the technological process [17-20].
As can be seen from the above-mentioned basic scientific theoretical explanations, during the process of hydrogen purification of petroleum distillates, depending on the composition of these distillates, gaseous substances of different composition, ecotoxic properties have high volatility and dissolve in high concentration in wastewater.
That is why every gas, liquid, solid waste formed during the process of hydrogen purification of petroleum distillates by the oil refining industry has a negative impact on the environment in various ways. One of the main directions of our scientific research is the ecological assessment of the environmental impact of wastewater formed in the process of hydrogen treatment of petroleum distillates.
Assigned indicator Amounts
Blurring, NTU 2.1
Color, mg/l Pt 1882
Total suspended solids, mg/l 6.0
Fluorides, mg/l 6.9
Phenols (spectrophotometric method), mg/l <0.03
Aluminum (Al), mg/l <0.02
Cobalt (Co), mg/l <0.008
Molybdenum (Mo), mg/l <0.005
Nickel (Ni), mg/l <0.008
Gas Chromatograph - Mass Spectrometer Analysis (Analysis of aromatic hydrocarbons in polystyrene
wastewater) General view of the chromatogram 1
A b u n d a n c e
2 5 0 0 0
2 4 0 0 0
2 3 0 0 0
2 2 0 0 0
2 10 0 0
2 0 0 0 0
9 0 0 0 8 0 0 0
7 0 0 0 6 0 0 0
5 0 0 0
4 0 0 0
3 0 0 0 2 0 0 0
10 0 0 0 0 0 0
9 0 0 0
8 0 0 0 7 0 0 0
6 0 0 0
5 0 0 0
4 0 0 0 3 0 0 0 2 0 0 0
10 0 0
TIC: 2 2 1 0 5 - 0 1 W A 3 .D \ d ata .m s 4
2 0 .0 0 2 5 .0 0 3 0 .0 0 3 5 .0 0 4 0 .0 0 4 5 .0 0
General view of the chromatogram 2
TIC: 2 2 1 0 5-0 1 W A3.D\data.ms
6 0 0 0 5 5 0 0 5 0 0 0 4 5 0 0 4 0 0 0 3 5 0 0 3 0 0 0 2 5 0 0 2 0 0 0 15 0 0 10 0 0
1 0.0 0 1 5.0 0 2 0.0 0 2 5.0 0 3 0.0 0 3 5.0 0 4 0.0 0 4 5.0 0 5 0.0 0
1,2,3,4,5- peaks of internal standard substances, these substances are used for calculations (1 - naphthalene-d8; 2 phenanthrene-d10; 3 - pyrene-d10; 4 - chryseneum-d12; 5 - perylene- d12).
10.00
1 5 . 0 0
Tim e - - >
Abundance
Tim e - - >
Abundance
2 4 0 0 0 2 2 0 0 0 2 0 0 0 0 1 8 0 0 0 1 6 0 0 0 1 4 0 0 0 1 2 0 0 0 1 0 0 0 0 8 0 0 0
Tim e -- >
TIC: 22105-0.1 WA3.D\data.ms
7.0 0 8.0 0 9.0 0 1 0.0 0 1 1.0 0 1 2.0 0 1 3.0 0 1 4.0 0 1 5.0 0 1 6.0 0 1 7.0 0
Fragment 1
Abundan ce
c
0)
c
28000 a
26000 0) 3
24000 c
22000 0) D
20000 r 0)
1 8000 a c
1 6000 0 !»
1 4000 r
1 2000 1 0000 0 N ®B
8000 C c
6000 »
4000 £ n c
2000 ■o a (0
TIC: 22105-01WA3.D\data.ms
»
r a
c m r a
T im e-->
1 8.00 1 9.00 20.00 2 1.00 22.00 23.00 24.00 25.00 26.00 27.00 28.00
Fragment 2
Abundance
S 5 0 0
5 0 0 0 8 5 0 0 8 0 0 0 7 5 0 0 7 0 0 0
6 5 0 0 6 0 0 0 5 5 0 0 5 0 0 0 4 5 0 0 4 0 0 0 3 5 0 0 3 0 0 0 2 5 0 0 2 0 0 0 15 0 0 10 0 0
5 0 0
TIC : 2 2 1 0 5 - 0 1 W A 3 .D \ data .m s
8 Yin's .Wh .Wn '0V 32 Yd' 33 Yd' 34 '0 V 3 5 '0 V 36 '0 V 37 '0V 38 '0 V 3 S '0 V 40 '0 V 41 .'ü ^ " 4 2 '0V
Tim e -->
Fragment 3
Results and discussion
The following explanations can be given about the results of the research:
- The rate of emission of each of the dissolved ecotoxicants into the atmosphere in the sample of the main industrial wastewater formed in the technological process of hydrogen purification of petroleum distillates was determined by spectral method.
- The reasons for the production of organic and inorganic volatile compounds in the wastewater of the hydrotreating process and our initial classification are given.
Rapid evaporation of volatile ecotoxicants from a sample of industrial wastewater during a study based on information on environmental and sanitary permissible concentration limits in
the technological literature, despite their short-term natural dilution in the atmosphere, each of which causes environmental pollution.
As it is known, even in the developed countries of the world, most of the wastewater treatment plants formed in the oil refining industry have an open surface, so volatile compounds of various compositions are released into the atmosphere from these plants.
Therefore, despite the environmental treatment of industrial wastewater generated in the oil industry, the presence of oil-dependent substances, phenol-type compounds in these waters, as well as the release of some of them into the water basins due to the above-mentioned volatile ecotoxicants have a negative environmental impact on flora and fauna.
2
At the same time, the evaporation of harmful substances from the industrial wastewater becomes a source of environmental pollution of the atmosphere, as well as the lithosphere.Thus, given the extensive information in the technical literature on the effects of each identified ecotoxicant on human health and the ecosphere, the biosphere in general, and their allowable concentrations in the industrial wastewater taken from the hydrogen treatment plant during the study, there is no need additional explanations of the impact of these substances on the environment.
Sampling of each of the gas, liquid and solid wastes formed in each of the processes of hydrogenation of petroleum oils and other petroleum distillates at the facility No 501 of the Heydar Aliyev Oil Refinery is carried out by various flexible, express and spectral methods. The analysis of the components is programmed by us.
Based on the determination of ecotoxi-cants contained in various types of waste generated in the facility depending on the composition of raw materials of technological processes the assessment of environmental impact can be considered scientifically based.
Conclusions
According to the results of the research, it can be noted that the industrial wastewater discharged from the oil refinery's facility No 501 has a content that will damage the eco-sphere and biosphere, despite the fact that the discharge standards meet the permissible discharge limits.
As a result of our analysis of the composition of these waters, polycyclic aromatic hydrocarbons and other harmful substances in the wastewater, no matter how much the harmful elements in the waste water are cleaned, they remain dissolved in the water and dumped into water bodies. Over many years, these small amounts can cause huge damage. Accumulation of these elements in the bottom sediments damages the aquatic life in the waters and as a result of leaks, the lithosphere is also exposed to pollution.
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NEFT YAGLARININ HiDROGENLO TOMiZLONMOSi PROSESiNDOYARANAN TULLANTI SULARININ TORKiBiNDO OLAN EKOTOKSiKANT MADDOLORiN SPEKTRAL ÜSULLARLA TOYiNi
A.M.Hüseynli, Q.i.Bayramov
Maqalada neft yaglarinin hidrogenla tamizlanmasi prosesi zamani alinmi§ sanaye girkab sulanndan götürülmü§ nümunada hall olunmu§ ekotoksikantlarin miqdannin tayini tahlil edilir. Hidrogenla§ma prosesi zamani neft distillatlarinin tarkibinda olan har bir birla§manin tabiatindan asili olaraq müxtalif növ tullantilar amala galir. Neft emali sanayesi tarafindan neft distillatlarinin hidrogenla tamizlanmasi prosesi zamani amala galan har bir qaz, maye, bark tullantilar atraf mühita müxtalif yollarla manfi tasir göstarir. Elmi tadqiqatlarimizin asas istiqamatlarindan biri neft distillatlarinin hidrogenla tamizlanmasi prosesinda amala galan tullanti sularinin atraf mühita tasirinin ekoloji qiymatlandirilmasidir. Alinmi§ naticalar asasinda tullanti sularinin atraf mühita tasiri qiymatlandirilmi§dir Qirkab su nümunasindaki ugucu ekotoksikantlarin miqdari spektral üsullarla müayyan edilmi§ va cadvalda göstarilmi§dir Biz polisiklik aromatik karbohidrogenlar ügün qaz xromatoqrafiyasi-kütlavi spektrometriya metodundan; metallar ügün optik emissiya spektrometriya üsulu; fenollar, boyalar va flüor ügün spektrometriya üsulu; bulaniqliq ügün nefelometriya üsulu; ümumi asili hissaciklar ügün qravimetriya üsulundan istifada etmi§ik. Alinmi§ naticalar asasinda hidrogen tamizlayici qurguda texnoloji proses zamani amala galan tullanti sularinin atraf mühita tasirini qiymatlandirmak mümkündür. Ara§dirmalarin naticalarina asasan qeyd etmak olar ki, NEZ-in (neft emali zavodu) 501 nömrali qurgusundan atilan sanaye tullanti sulari tullanti standartlarinin buraxila bilan axinti normalarina uygun olmasina baxmayaraq, ekosfera va biosfera zarar veracak tarkiba malikdir.
Agar sözlzr: Neft distillatlari, hidrogenla tamizlama, spektral metod,ekotoksikant maddalar, tullanti sulari.
