Environmentally benign chemical

Transcription

1 Environmentally benign chemical processes (EBChemP) Reducing volatile organic compunds, IPPC and BATs Edit Székely, Erika Vági BME, Department of Chemical and Environmental Process Engineering

2 Topics to be covered EU directive What are the possibilities? Case studies Regulations and improvements Case studies

3 VOC Solvents Emissions Directive (Directive 1999/13/EC) A sites to check: /legislation.htm The emissions of volatile organic compounds (VOCs) in the atmosphere contribute to the formation of the tropospheric ozone (ozone in the lower atmosphere). Large quantities of this ozone may be harmful to people, vegetation, forests and crops. Sensitive people may suffer irritation of the throat and eyes, as well as respiratory difficulties. Tropospheric ozone is also a greenhouse gas.

4 Type of emissions Point emission Point sources are localized, large, stationary sources of air/water or soil emissions such as factories, power plants, foundries, refineries, and chemical plants. Monitored and quantified. Diffuse emission Many smaller and dispersed sources of pollution released into soil, water or air. Difficult to monitor and to quantify.

5 Fields covered Adhesive coating Any activity in which an adhesive is applied to a surface, with the exception of adhesive coating and laminating associated with printing activities. Coating activity Coil coating Any activity where coiled steel, stainless steel, coated steel, copper alloys or aluminium strip is coated with either a film forming or laminate coating in a continuous process.

6 Dry cleaning Any industrial or commercial activity using VOCs in an installation to clean garments, furnishing and similar consumer goods with the exception of the manual removal of stains and spots in the textile and clothing industry. Footwear manufacture Manufacturing of coating, varnishes, inks and adhesives

7 Manufacturing of pharmaceutical products The chemical synthesis, fermentation, extraction, formulation and finishing of pharmaceutical products and where carried out at the same site, the manufacture of intermediate products. Surface cleaning Any activity except dry cleaning using organic solvents to remove contamination from the surface of material including degreasing. A cleaning activity consisting of more than one step before or after any other activity shall be considered as one surface cleaning activity. This activity does not refer to the cleaning of the equipment but to the cleaning of the surface of products.

8 Printing Vegetable oil and animal fat extraction and vegetable oil refining activities Any activity to extract vegetable oil from seeds and other vegetable matter, the processing of dry residues to produce animal feed, the purification of fats and vegetable oils derived from seeds, vegetable matter and/or animal matter. Vehicle refinishing Any industrial or commercial coating activity and associated degreasing

9 Requirements The industrial operators concerned can conform to the specified emission limits in either of the following ways: by installing equipment to reduce emissions to comply with the emission limit values and the fugitive emission values, or total emission limit values; by introducing a reduction scheme to arrive at an equivalent emission level, in particular by replacing conventional products which are high in solvents with low-solvent or solvent-free products. Solvents or mixtures likely to have a serious effect on human health because of their content of VOCs (classified as carcinogens, mutagens, or toxic to reproduction), must be replaced by less harmful substances or mixtures.

10 Requirements for Member States National plans Substitution Monitoring Reports

11 Pharma industry The activity manufacturing of pharmaceutical products is defined as synthesis, fermentation, extraction, formulation and finishing of pharmaceutical products and where carried out at the same site, the manufacture of intermediate products. The SE Directive covers installations in which this activity is taking place with an annual organic solvent consumption greater than 50t.

12 Solvent consuming operations in the pharma industries Synthesis (solvent of reactants, e.g. ethanol, methanol, isopropanol, dichloro-methane) Fermentation (separation of product) Extraction, leaching (e.g. ethanol, methanol, toluene, heptane) Drying, mixing, pelleting, granulation Tablet coating (pl. ethanol, methanol, isopropanol, dichloro-methane) Cleaning of equipment (e.g. methanol) Storage site.

13 Possibilities of substitution Special reduction requirements for CMR (Carcinogenic, Mutagenic or Toxic for Reproduction) solvents Possible substitutions: Synthesis, extraction (IPR, GMP, technological limitations may arise) Cleaning of equipment with water based solutions Tablet coating (aqueous, powder e.g. technologies)

14 Reduction of emission 1. Condensation (solvent recycling might be viable) Cryogen condensation (in case of expensive solvents) Recycling of solvent (in-house or through a specialized company) Adsorption Absorption

15 Reduction of emission 2. Thermal oxidation (from 1-2 g VOC / Nm 3 sustainable. Around 800 C) Catalytic oxidation ( C, good at constant solvent feed) Biooxidation Process improvements Organisational measures

16 Process improvements Collection of VOCs from different distributed sources using local exhaust ventilation hoods, for subsequent control of point and fugitive emissions Working at greater concentration to reduce the consumption of solvents Modification of operating conditions for distillation (e.g. distillation under ordinary pressure instead of vacuum distillation) Improved condenser efficiency (e.g. increased exchanger surfaces and refrigerating capacities) Using dry-sealed vacuum pumps instead of liquid ring vacuum pumps Implementing leak prevention systems Better control of reaction parameters (feed rate, mixing, temperature) Optimization of process parameters

17 Process improvements Using closed pressure filters or vacuum filters that are more leak free than open filters Using vacuum dryers with enhanced solvent condensation Fitting pressure vacuum relief valves to storage tanks Back venting to the delivery tanks during bulk storage tank filling Improved exhaust air collection systems Using closed or covered mixing systems Using closed containers for the transport and intermediate storage of solvents Using closed-loop liquid and gas collection equipment for cleaning of reactors and other equipment

18 Organisational measures Effective production and maintenance; Reduction of the number of batches and increasing batch capacity; Reduced quantity of stored solvents Employee training on solvent awareness including on guidance on effective handling and storage Thorough solvent auditing (mass balance i.e. examine solvent route).

19 Vegetable oil industry >10 t annually

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21 Hexane content

22 Substitution of hexane Relevant - health and safety issues. Emerging technologies are only economical for high added value products (e.g. sesame oil) SFE Enzymatic extraction Sonification Osmotic shock

23 Reduction of emission similar possibilities as in pharma industry condensation recycling process improvement organisation measures

24 Dry cleaning There are approximately 58,000 dry cleaning installations in the EU, 60 to 90 % of the European textile care companies still use Perc (Perchloroethylene (Cl2C=CCl2 or Perc)) but it is expected that the proportion in professional cleaning will decrease.

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26 Alternative solvents/technologies liquid silicone hydrocarbons supercritical CO2 drying water based processes

27 Conclusions VOC substitution have to be examined in each cases There are general applicable methods to reduce emission Careful technology management Inventory Localization of emission sources, treatment of the streams Economic question.

28 The IPPC directive Integrated Pollution Prevention and Control The European Integrated Pollution Prevention and Control (IPPC) Bureau was set up to organise an exchange of information between Member States and industry on Best Available Techniques (BAT), associated monitoring and developments in them. The IPPC Directive is based on several principles, namely (1) an integrated approach, (2) best available techniques, (3) flexibility and (4) public participation. 1. The integrated approach means that the permits must take into account the whole environmental performance of the plant, covering e.g. emissions to air, water and land, generation of waste, use of raw materials, energy efficiency, noise, prevention of accidents, and restoration of the site upon closure. The purpose of the Directive is to ensure a high level of protection of the environment taken as a whole.

29 The IPPC directive 3. The IPPC Directive contains elements of flexibility by allowing the licensing authorities, in determining permit conditions, to take into account: (a) the technical characteristics of the installation, (b) its geographical location and (c) the local environmental conditions. 4. The Directive ensures that the public has a right to participate in the decision making process, and to be informed of its consequences, by having access to (a) permit applications in order to give opinions, (b) permits, (c) results of the monitoring of releases and (d) the European Pollutant Release and Transfer Register (E-PRTR). In E- PRTR, emission data reported by Member States are made accessible in a public register, which is intended to provide environmental information on major industrial activities. E-PRTR has replaced the previous EU-wide pollutant inventory, the so-called European Pollutant Emission Register (EPER).

30 Use of E-PRTP

31 Example: Transfer to waste-water

32 BAT = Best available technique B best in relation to techniques, means the most effective in achieving a high general level of protection of the environment as a whole A available techniques means those techniques developed on a scale which allows implementation in the relevant class of activity under economically the technically viable conditions, taking into consideration the costs and advantages, whether or not the techniques are used or produced within the State, as long as they are reasonably accessible to the person carrying out the activity T techniques includes both the technology used and the way in which the installation is designed, built, managed, maintained, operated and decommissioned.

33 How to apply BAT? At the installation/facility level, the most appropriate techniques will depend on local factors. A local assessment of the costs and benefits of the available options may be needed to establish the best option. The choice may be justified on: the technical characteristics of the installation/facility its geographical location local environmental considerations the economic and technical viability of upgrading existing installations

34 Etc. BREF = Best available technique reference document BREF in the Cement and Lime Manufacturing Industries BREF for the Ceramic Industry BREF in the Chlor-Alkali Manufacturing Industry BREF in Common Waste Water and Waste Gas Treatment/Managment Systems in the Chemical Sector BREF to Industrial Cooling Systems BREF on Large Combustion Plants BREF on the Production of Iron and Steel BREF on Large Volume Inorganic Chemicals - Ammonia, Acids & Fertilisers BREF for Large Volume Inorganic Chemicals - Solids & Others BREF in the Large Volume Organic Chemicals Industry BREF for Organic Fine Chemicals BREF for the Production of Polymers BREF in the Pulp and Paper Industry BREF for Mineral Oil and Gas Refineries BREF for Speciality Inorganic Chemicals BREF for Surface Treatment of Metals & Plastics BREF for Surface Treatments Using Organic Solvents BREF for the Textiles Industry BREF for the Waste Treatments Industries

35 Indexes of a typical BREF Executive summary Preface Scope 1. General information 2. Applied processes and techniques 3. Current emission and consumption levels 4. Techniques to consider in the determination of BAT 5. Best available techniques 6. Emerging techniques 7. Concluding remarks Glossary Annexes

36 Air pollutants

37 IPPC Reference document on BATs for the Manufacture of Large Volume Inorganic Chemicals Ammonia, Acids and Fertilisers, 2007.

38 Production of nitric acid One of the top ten industrial chemicals. In million tonnes of HNO3 were produced in EU. The largest market for nitric acid is the production of ammonium nitrate (AN) and calcium ammonium nitrate (CAN), accounting for almost 77% of the total world consumption of nitric acid in HNO3 is also used for manufacture AN explosives; Chemicals (caprolactam, adipic acid, dinitro toluene, nitrobenzene). Metal treatment; Uranium processing.

39 Main environmental concerns Oxidation of NH3 generates NO, with N2O as a byproduct. N2O emission level depends on the technology applied (average: 6kg N2O/ tonne of HNO3). Four relevant plant types are distinguised:

40 Production of HNO3 Oxidation of NH3 Oxidation of NO and absorption in H2O NO dependence on P and T

41 Production of nitric acid (with BAT)

42 Catalytic reactor Catalyst: Rh (5-10 %), main component Pt, sometimes 5-10 % Pd. NH3 to air ratio is dominant. Stoechiometric: 13.5 %, but % is typical. The higher temperature the lower the N 2 O production (decomposition to N 2 and O 2 ).

43 Effluent before purification Tail gas properties after the absorption stage

44 Possibilities to reduce NO x and N 2 O emission NO x Optimisation of absorption step SCR (Selective Catalytic Reduction) NSCR (Non-selective Catalytic Reduction) Adding H 2 O 2 at absorption Combined purification of the effluent N 2 O Improved filtration Improved mixing Monitoring of the catalyst activity Optimisation of ammonia to air ratio ( % NH3) Reduction of N 2 O Combined purification of the effluent

45 Reduction of N 2 O with a longer reactor Higher temperature ( C) 3.5 m 7 m empty pipe (d< 4 m) added Increased avarage residence time ( with1-3 s) (decrease by % to 400 ppm or to 2-3 kg N 2 O/ ton 100%-os HNO 3 )

46 Reduction of N 2 O by a catalyst Possible also in older reactors De-N2O catalyst: oxides e.g Ce, Zn, Cu, Al oxides and mixtures (developed by Yara, BASF or Heraus) Increased pressure drop Additional cost for the catalyst T = C Decrease of N2O to 325 ppm

47 Combined technique NO x and N 2 O Installed between final tail gas heater and the tail gas turbine. Operates at C. With two catalyst layers (Fe zeolite) + intermediate injection of NH3. N2O and NOx removal efficiency of 99% NOx emission levels < 5 ppm Applied for new plants or older plants with tail gas T > 420 C.

48 Combined technique NO x and N 2 O Emerging technique for reducing NOx and N2O emissions If NOx eliminated by reaction with NH3 in the first step. N2O removed by catalytic reduction with HC (natural gas or propane). Simultane reduction of N2O and NOx as previous set-up. No information on other pollutants. For plants with tail gase temperatures of C.

49 Total greenhouse gas emission Facts and Figures of the European Chemical Industry, 2017, and M tonnes in 1990, 3.95 M tonnes in 2018

50 Date of presentation: 24 April Time: 5-7 minutes per person Task: Presentation task Select one BREF document ( and prepare a presentation, which is interesting for all students in the class. Make them interested in the topic, aim to teach something you found excited. It is suggested to follow the scheme below: - title slide (title of presentation, your name) - one slide to give a general introduction to the typical production technology, emphasize the typical reasons and sources of environmental pollution, emissions slides to explain one complex or some more simple BAT solutions for the presented problems - one conclusion slide and take home message. SEND ME the title of chosen topics in advance (by 1st of April), please!!!!

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