Hazop Analysis of a Bioprocess for Polyhydroxyalkanoate (PHA) Production from Organic Waste: Part A
Abstract
:1. Introduction
- During the design phase in order to check that safety objectives are correctly met;
- Before start-up in order to verify the adequacy of operational and emergency procedures;
- During the operation in order to assess the impact on safety of maintenance operations or any modification to the installation.
- (1)
- To verify the project safety;
- (2)
- To check operating and safety procedures;
- (3)
- To increase the safety of an existing system;
- (4)
- To verify that safety equipment is working in the best possible way.
- Operating procedures development;
- Verification of design values, process parameters and possible modifications;
- Request for additional alarms;
- Request for unforeseen alarms or blocks;
- Useful information for assessing and managing the risk associated with the accidental identified events.
2. Materials and Methods
2.1. HAZOP Analysis
- Definition of the purpose and objectives of the study;
- Team selection;
- Study preparation;
- Carrying out the analysis;
- Recording the results.
2.2. HAZOP Methodology
- The examination must be systematic;
- The analysis must be carried out with a degree of formality (forms, etc.), so that the reasons for each decision made during the analysis can be clearly identified by different people at different times;
- All working on the implementation of the project must be involved in the analysis.
- A checklist;
- An ad hoc HAZOP method (BioHazOp).
2.2.1. The Checklist
- Process specification section (substances hazard classification, biohazard, flammability, explosivity, relevant parameters, etc.);
- General section (management outline): operating procedures, plant layout, emergency response/on-going programs and process hazard analysis.
2.2.2. BioHazOp
2.3. Piping and Instrumentation Diagram (P&ID)
- Mechanical equipment (vessel, tanks, pumps, etc.);
- Valves and their identification;
- Process piping;
- Flows directions;
- Vents;
- Drains;
- Physical sequence of equipment;
- Interconnections;
- Instrumentation (level, temperature and pressure transmitters, etc.).
3. Case-Study: Pilot Plant for the PHA Production
- Acidogenic fermentation of the organic feedstock for volatile fatty acids (VFA) production;
- PHA-storing microorganisms’ selection from MMC;
- PHA accumulation maximization.
- Caxial centrifuge equipped with a 5.0 μm porosity nylon filter bag (first stage);
- Ultrafiltration membrane with 0.2 μm porosity (second stage).
4. Results
4.1. Relevant Deviation Matrices and BioHazOp Worksheets
4.2. Piping and Instrumentation Diagrams
- F (flow rate);
- P (pressure);
- L (level);
- T (temperature).
- I (indicator);
- C (controller);
- T (transmitter).
5. Discussion
- Periodic check of their side covers. In case of leakages, the screws must be re-tightened, or gaskets must be replaced;
- Hydraulic damper check (lubricant level). In particular, it is recommended to use lubricant, which has a kinematic viscosity ranged between 30 and 50 mm2/s (ISO grade);
- Check of hydraulic circuit connections (all the components have to be perfectly tightened).
6. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Acknowledgments
Conflicts of Interest
References
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Process Unit | ||||
---|---|---|---|---|
Engineering process causes consequences | Biotechnology process causes consequences | Existing counter measures | Biohazard | Proposed counter measures |
process parameter | ||||
deviation 1 | ||||
deviation 2 | ||||
deviation n |
HRT | Window Time (d) | Feedstock (v/v%) | T (°C) | pH | Hydrolysis (°C, h) |
---|---|---|---|---|---|
5–6 | 140–420 | SS(30%)-OFMSW(70%) | 37 | uncontrolled | 72 °C, 48 h |
Run | HRT (d) | SRT (d) | OLR (g COD/L d) | CL (d) | SRT/CL (d/d) | Feeding Frequency (d−1) | Operation Length (d) | Load Per Cycle (g COD/L) |
---|---|---|---|---|---|---|---|---|
Ae3 | 1 | 1 | 4 | 0.5 | 2 | 2 | 45 | 20 |
The anaerobic reactor (fermenter) contains VFA with acetic and butyric acids as the main components. It continuously works by processing up to 380 L/5 days of mixture. Some substances in the mixture are hazardous from a toxic or fire standpoint. More in detail, the mixture contains: - Biological agents including bacteria, microfungi and protozoa. With reference to infective risk, the biological agents have been classified according to the Annex III of Directive 2000/54/EC [27] as amended by Directives 2019/1833/EC [29] and 2020/739/EC [30]; - Chemical agents consisting of VFA (acetic acid, propionic acid, butyric acid, valeric acid, isobutyric acid, isovaleric acid, caproic acid, isocaproic acid and heptanoic acid) and gases (carbon dioxide, hydrogen, methane, hydrogen sulphide). Such substances pose physical hazards and/or health hazards according to the [28] EC Regulation 1272/2008 (CLP Regulation) classification criteria. The products of any dangerous reactions may include alcohols, organic macromolecules and gaseous products. A biowaste pre-treatment is applied to the process. Unwanted reactions may be caused by abnormal process conditions (e.g., temperature, pH), abnormal flow rates, system failure (oxygen inlet), electric equipment malfunction (e.g., sensors), mechanical failure (e.g., pump or stirrer trip), etc. Moreover, hazard can be also due to loss of containment. The process equipment includes relief systems (hydraulic seal protected against freezing through antifreeze liquid) and drains (sampling points). The process does not work in or near the flammability range. Further detailed information has been acquired with respect to the following: |
- BIOHAZARD: the biological agents, involved in the hydrolytic and acidogenic steps, include bacterial genera such as Clostridium, Bacillus, Peptococcus, Vibrio, Enterococcus, Lactobacillus, Ruminococcus, Butyribacterium, Propionibacterium, Micrococcus, etc., fungi (Phycomicetes, Ascomycetes) and protozoa. The thermal biowaste pretreatment (70 °C) and mixing are able to inactivate completely fecal indicator bacteria (fecal coliform, Salmonella spp., and fecal Streptococcus), within 80 min. According to Directive 2000/54/EC [27], regarding the infectious risk, the microorganisms, which take part in the acidogenic fermentation, are mainly assigned to the risk group 1 and to a small extent of the risk group 2 (low pathogenicity). Some of the risk group 2 microorganisms should be considered opportunistic agents. Furthermore, one should take into account the sensitizing and toxic risk related to the exposure to biological agents in bioaerosol and biological components conveyed such as particulates (i.e., bacterial endotoxins, fungal spores) during some process activities. The organic waste is automatically fed to the fermenter continuously or semi-continuously (once a day) in containment conditions. During acidogenic fermentation, the microbial reactions take place in the closed bioreactor and, therefore, there is no workers exposure. However, activities, such as sampling for the monitoring of the fermentation process, could involve the workers exposure. Furthermore, some specific operations, such as handling of the electromechanical pumps, pipes, compressors, valves, drainage, cleaning and maintenance tasks, may pose exposure risks to bioaerosol. Therefore, the workers’ activities should be checked to define the exposure characteristics. The ways of penetration into the body are the gastrointestinal one (eg. hand-to-mouth contact), skin (eg contact through cuts), mucous membranes (splashes on nose, mouth, eyes) and inhalation (bioaerosol). The potential occupational exposure could be identified and documented through the biological environmental monitoring plan, but it is not mandatory according to Directive 2000/54/EC [27]. In order to prevent infectious workers risk, effective personal hygiene measures are sufficient, including the provision of adequate hand washing facilities. The sensitizing and toxic effects can be controlled by minimizing the generation of bioaerosols or dusts in the workplace. Where residual hazards/risks cannot be controlled by collective measures, the employer should provide for appropriate personal protective equipment, such as suitably fitted respiratory devices, when working in areas close to where bioaerosol is generated. |
- TOXICITY and ECOTOXICITY: the toxic agents in the main quantity are CH₃COOH (acetic acid, CAS No. 64-19-7) and CH3CH2CH2COOH (butyric acid, CAS No. 107-92-6), having potential health effects both acute and chronic. The substances entry routes are inhalation, skin contact and eye contact. Specific toxic effects are associated with each substance. So, the main toxic effects of acetic acid are: (1) Acute effects: increasing concentration involves increasing corrosive effects on skin and mucous membranes, and exposure to high concentrations causes severe damages to the eyes and the lungs. The oral intake of high concentrations can cause chemical burns in the digestive tract, metabolic disorders, blood impairment, cardiovascular reactions and renal damage; (2) Chronic effects: skin changes, chronic inflammation of eyes and respiratory tract, erosive tooth damage. Some substances (valeric acid, hydrogen sulfide) are ecotoxic for the aquatic systems. Preventive and protective measures include the use of gas detectors and of personal protective equipment for tasks involving the chemicals handling. |
- FLAMMABILITY & EXPLOSIVITY: the main components of the gaseous mixture are: CH4 (methane, CAS No. 74-82-8, H2S (hydrogen sulfide, CAS No. 7783-06-4) and H2 (hydrogen, CAS No. 1333-74-0). The operating overpressure and temperature are 20 mbar and 37 °C. The main condition, which has to be avoided, consists in the intake of O2 into the fermenter from the outside, even though there is no ATEX zone in the plant. The main preventive measure consists in the use of gases detection devices. |
Operating Procedure |
---|
There is no specific written procedure to maintain the on-going integrity of the process equipment. Nevertheless, good operating practices have been applied to carry out plant operations, such as cleaning of coaxial centrifuge and ultrafiltration membranes, and taking samples for laboratory analysis. |
Plant layout |
There are buffer zones between the plant and the external public (population). The pilot plant operators are potentially exposed to hazards from the wastewater treatment plant within which the PHA production process takes place. The OFMSW transfer to digester is carried out under containment conditions and therefore it has no impact on the environment and operators. The workplace layout includes the location of control rooms, laboratories and offices, drainage areas and sampling points. |
Emergency/ongoing program |
A number of steps in the production process is managed by programmable logic controller (PLC). There is no system which ensures the plant is currently kept and periodically tested. |
Management-Process Hazard Analysis (PHA) |
No risk analysis techniques other than BioHazop analysis (FTA, FMEA, What if, etc.) have been applied to the plant. BioHazop addresses the following: - Hazards of the process; - Process equipment; - Engineering and administrative controls; - Consequences of failure for engineering or administrative controls, including consequences of deviation and steps required to correct or avoid the deviation; - A qualitative evaluation of safety and health effects (of failures) on employees in the workplace. The BioHazop analysis has been performed by a team that had the expertise: - In engineering and process operations; - In the BioHazop evaluation methodology; - In biological and chemical (health and safety issues) risk assessment. |
Parameter | Reasons for Exclusion |
---|---|
Run duration | The fermentation continues until the feedstock input mixture is consumed. In order to produce representative data, the fermentative process must last for at least 20–25 days (corresponding to 3–4 HRT) |
Chemical oxygen demand (COD) | The parameter is not definable. It depends on the feedstock (OFMSW) carbon content variability throughout the year and therefore it is out of control for the process operability |
Oxidation-reduction potential | the parameter is not measured in the pilot plant |
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Share and Cite
Lauri, R.; Incocciati, E.; Pietrangeli, B.; Tayou, L.N.; Valentino, F.; Gottardo, M.; Majone, M. Hazop Analysis of a Bioprocess for Polyhydroxyalkanoate (PHA) Production from Organic Waste: Part A. Fermentation 2023, 9, 99. https://doi.org/10.3390/fermentation9020099
Lauri R, Incocciati E, Pietrangeli B, Tayou LN, Valentino F, Gottardo M, Majone M. Hazop Analysis of a Bioprocess for Polyhydroxyalkanoate (PHA) Production from Organic Waste: Part A. Fermentation. 2023; 9(2):99. https://doi.org/10.3390/fermentation9020099
Chicago/Turabian StyleLauri, Roberto, Emma Incocciati, Biancamaria Pietrangeli, Lionel Nguemna Tayou, Francesco Valentino, Marco Gottardo, and Mauro Majone. 2023. "Hazop Analysis of a Bioprocess for Polyhydroxyalkanoate (PHA) Production from Organic Waste: Part A" Fermentation 9, no. 2: 99. https://doi.org/10.3390/fermentation9020099