Presentation on theme: "Chapter 3 Evaluation of Methods to Design Safer Chemicals."— Presentation transcript:
Chapter 3 Evaluation of Methods to Design Safer Chemicals
DfE developed the Standard for Safer Cleaning Products (SSCP) to make the DfE Criteria for recognition under the EPA Safer Product Labeling Program more transparent and accessible to potential partners and stakeholders. A group convened under the Green Chemistry and Commerce Council provided guidance to DfE for the development of this document. DfE's Standard for Safer Cleaning Products (SSCP) DfE's Standard and Criteria for Safer Chemical Ingredients
Each ingredient in a formulation has a function in making a product work - whether it is to aid in cleaning by reducing surface tension (surfactants), dissolve or suspend materials (solvents), reduce water hardness (chelating agents), or provide a scent (fragrances). Within these "functional classes," many ingredients share similar toxicological and environmental fate characteristics. As a result, DfE focuses its review of formulation ingredients on the key (environmental and human health) characteristics of concern within a functional class. This approach allows formulators to use those ingredients with the lowest hazard in their functional class, while still formulating high-performing products. DfE Criteria for Safer Chemical Ingredients
The DfE Safer Product Labeling Program evaluates each ingredient in a formulation against the following Master and Functional-Class Criteria documents, as appropriate. These documents define the characteristics and toxicity thresholds for ingredients that are acceptable in DfE-labeled products. The Criteria are based on EPA expertise in evaluating the physical and toxicological properties of chemicals, and while they incorporate authoritative lists of chemicals of concern, they go far beyond these lists. DfE applies the Criteria using EPA research and analytical methods to ensure that DfE-labeled products contain only the safest possible ingredients. All Criteria documents are part of DfE's Standard for Safer Cleaning Products (SSCP).
Functional-class criteria define and more fully explore the safer end of specific ingredient-class continuums. Using the Master Criteria as a guide, the functional-class criteria tailor the health and environmental endpoints in the Master Criteria in a way appropriate to the specific functional class, designate key distinguishing characteristics and adjust thresholds as necessary. Developing the Criteria improves the general understanding of the characteristics of safer ingredients in the class and helps identify green-chemistry opportunities and successes. Functional-Class Criteria
Surfactants in cleaning products are distinguished by their rate of biodegradation, degradation products, and level of aquatic toxicity. The DfE Criteria for Surfactants combine these hazard characteristics, and requires that surfactants with higher aquatic toxicity demonstrate a faster rate of biodegradation without degradation to products of concern. Surfactants that meet the Criteria are acceptable for use in a DfE-labeled cleaning product; surfactants in products which typically by-pass sewage treatment must meet the Criteria for Environmental Fate & Toxicity for Chemicals in Direct Release Products. DfE Criteria for Surfactants
With cleaning solvents, there are potential concerns for the following hazards: carcinogenicity, acute mammalian toxicity, reproductive and developmental toxicity, repeated-dose toxicity, neurotoxicity, and environmental fate and toxicity. The DfE Criteria for Solvents (PDF) (13 pp, 454K, About PDF) were developed for the alcohol, ester, ethylene glycol ether, and propylene glycol ethers solvent classes. Structural definitions of these classes are included in the Criteria document. DfE Criteria for Solvents
These Criteria were developed to identify safer chelating and sequestering agents, which have preferred human and environmental health profiles. DfE developed the Criteria with a group of stakeholders that included chelating agent manufacturers, cleaning product formulators, environmental non-governmental organizations, certification groups, industry associations, and others. Chelating and sequestering agents that pass these Criteria can be included in cleaning products eligible for recognition under the DfE Safer Product Labeling Program. DfE Criteria for Chelating and Sequestering Agents
The Criteria for Chelating and Sequestering Agents sets a high bar to which some product manufacturers may need to adapt. To allow time for formulation changes, DfE has developed the following implementation schedule.
Product manufacturers who submit products on or after this date must meet the new criteria. The new criteria would apply as follows: To candidate partners and products as a condition of partnership; To existing partners with candidate products as a condition of adding the products to the partnership; and To existing partners and products within one year from this date, effective on the anniversary of their partnership and coinciding with their annual audit. December 31, 2011
Chelating agents in candidate products will be reviewed based on the new Criteria and manufacturers will be informed of product review status. The purpose of this interim review is to give fair notice to the ingredient and product formulating communities and to guide their transition to safer alternatives, as necessary. Now to December 31, 2011
The DfE Criteria for Fragrances was developed by the DfE Program and a group of stakeholders that included the fragrance industry, cleaning product formulators, environmental non-governmental organizations, and others. These Criteria are designed to identify safer aroma chemicals and fragrance formulations for use in cleaning products. While Version 1 of the Criteria focused on human health considerations associated with fragrances, Version 2 of the Criteria addresses both human health, and environmental fate and effects. DfE Criteria for Fragrances
More than 2,000 chemical substances with diverse chemical structures, and therefore diverse human and environmental health profiles, are used in formulation by the fragrance industry. To identify safer chemicals for this diverse set of raw materials, a range of human and environmental health endpoints serve as the basis for screening out fragrance raw materials of concern. A fragrance must meet all requirements for each hazard endpoint in order to meet the Criteria.
Given the complexity of fragrance formulations, DfE recognizes that implementing the Criteria may be challenging for formulators and their suppliers. DfE's third-party profilers will begin using the Criteria to evaluate fragrances in candidate products for recognition and providing feedback to formulators. DfE will require that labeled and candidate products meet the Criteria according to the following schedule.
December 31, 2011 Product manufacturers who submit products on or after this date have to meet the new criteria. The new criteria would apply as follows: To candidate partners and products as a condition of partnership; To existing partners with candidate products as a condition of adding the products to the partnership; To existing partners and products within one year from this date, effective on the anniversary of their partnership and coinciding with their annual audit.
During this transition period, the new Criteria will be used to provide feedback to manufacturers on product status. The purpose of this interim review is to give fair notice to the ingredient and product formulating communities and to guide their transition to safer alternatives, as necessary. Now to December 31, 2011
Criteria for Environmental Toxicity and Fate for Chemicals in Direct Release Products Certain products intended for use outdoors are likely to bypass sewage treatment, llimiting the time for degradation prior to entering sensitive environments. For these products, like boat cleaners and graffiti removers, DfE has raised the bar in its standard environmental criteria to address the potential for immediate contact with aquatic life. Any ingredients (including surfactants, preservatives, solvents, etc.) that have aquatic toxicity values <1 mg/L are not allowed in DfE-recognized direct release products.
DfE Considerations for Microorganism-based Products Microorganism-based products are a distinct class and subject to tailored evaluation criteria. In its review, DfE carefully considers the identity and potential hazards and risks of the microbial species, as informed by its Checklist for Formulations Containing Microorganisms PDF (7 pp, 29K, About PDF), in combination with other considerations like purity of strain, ingredient functionality and product performance, as described in its Considerations for Microorganism-based Products (5 pp, 876K, About PDF). Please note that microbial-based products intended for use in indoor environments are not eligible for partnership, as explained in the Considerations document. Non-microbial ingredients will be reviewed based on their respective component- class criteria.
DfE Criteria for Ice-Melt Products An ice-melt product under DfE is, as the name implies, one that melts ice and snow at temperatures below the freezing point of water, and not simply a product that aids traction like sand. A manufacturer of a safer ice-melt product may become a DfE partner provided that they agree to certain terms in their partnership agreement and that their product has the characteristics specified below.
Pass the appropriate DfE safer chemical criteria Reduce sodium (Na) and chloride (Cl) use by at least 30% (under comparable use scenarios). Be labeled under a DfE partnership agreement in which the product manufacturer has agreed to a customer education/training plan to ensure proper product use and application rates (and reductions in Na and Cl). Not contain cyanide as an anti-caking agent. Function at temperatures < 0 F.
Comply with Pacific NW Snow Fighters’ criteria for reduction in corrosivity to steel: to be acceptable, a corrosion-inhibition chemical product must prove to have a percent effectiveness value of at least 70% less than Sodium Chloride). Meet performance levels as evaluated under the Pacific NW Snow Fighters’ criteria.
Clean Gredients Formulators who subscribe to the Clean Gredients? database can find a list of surfactants, solvents, chelating and sequestering agents, and fragrances that meet DfE's Criteria. Suppliers who subscribe can have their chemicals reviewed against the appropriate criteria and listed in the database. Nearly 300 formulators are finding safer ingredients on Clean Gredients.
Catalysis: Concepts and Green Applications Industrial ecology Green engineering Green chemistry Renewable energy Practical approaches Sustainable development Strategic goal Life-cycle assessment Catalysis Waste management E-factor, atom economy Process intensification Operational tools Monitoring tools
Oxidation of diphenylmethanol to benzophenone
Relative efficiency of various engine types % Efficiency Gas electric Diesel electric Micro- turbine Hydrogen fuel cell Costs of obtaining hydrogen
The traditional propene oxide route
The SMPO process Catalytic oxidation of propene
The four stages of life-cycle assessment Life-cycle assessment Defining the scope Inventory analysis Impact analysis Improvement analysis Stage 1Stage 2Stage 3Stage 4
Different types of catalysts copper-zinc crystallites on silica zeolite (crystalline aluminosilicate ) enzyme (biocatalyst)
Examples of chemo- and diastereoselectivity Regioselectivity Enantioselectivity
Base-catalysed transesterification of triglycerides
Green Solvents and Ionic Liquids Waterless Cleaning LLC is 100 % owned by Stan Seelig and Tony O’Lenick, with combined 60 years of industrial/consumer experience in cleaning/personal care. Mission Statement To provide green/sustainable cleaning formulations using “green” solvents and ionic liquid co-solvents for the replacement of wasteful, water-based formulations and practices. Company Vision 1.To license green and sustainable solvent-based cleaning formulations to industry. 2.To sell specialty ionic liquids that provide multiple benefits for a lower overall cost into cleaning/other markets.
What are “Green” Solvents ? (for our applications) Not halogenated, non-flammable (< 100 0C), non-hazardous, non-toxic Low /no VOC BP <200 0C Biodegradable, stable, recyclable Low water solubility (< 5 wt% in solvent) Best choices are solvents derived from bio-diesel, plant, natural products
Choosing the Right Green Solvent(s) Considerations Low pricing (<$ 1.50/lb) World-wide availability, high volume potential Safe for people /environment Low /no VOC Compatibilities (w/equipment /materials to be cleaned) Equipment design Examples –dibasic esters, lactates, soy-based, Si-based, others
What are Ionic Liquids (ILS) ? OurILs are: Combinations of cations(+) and anions(-) Liquids (viscous) at room temperature (RTILs) Cross between “Green” solvents and surfactants Hydrophobic, non-halogenated, no unusual cyclic structures, conductive, simple Less expensive (ours $100/gm)
Applications for Ionic Liquids Solvents for pharmaceutical manufacturing Lubricants Extending the life of a lithium battery Dispersants in paints Solar energy (heat transfer and storage medium) Electrochemical applications Cleaning and drying
Primary Project To develop a revolutionary change in the cleaning of fabrics by combining dry cleaning concepts and water- based laundry systems into a green and sustainable laundry system for institutional, industrial, commercial, and consumer laundry operations (without using water) This is a Disruptive Technology !
Laundry Cleaning Today Follows the Energy Star program by minimizing: Water usages Energy consumption Chemical usage Overall costs But, we still dump billions of gallons of water down the drain every day (containing more detergent than contamination ) ! Is this a Sustainable Process ?
Is water, the Next Oil ? 3% of the Earth has drinkable water 1% of the 3% is accessible (rest is tied up in glaciers) 20% of the 1% is found in the Great Lakes Region (USA) Ethical Challenge: We need to minimize our use of drinking water for non-essential applications (i.e., laundry, dishwasher, toilets, watering lawns, washing cars, etc). Our waste water streams are running on maximum.
Laundry Cleaning Tomorrow Moving towards Waterless (Dry) Cleaning Cold water cleaning w/minimal water and energy Cleaning w/ozone (O3injected water reduces heat), 2003 Self cleaning laundry (coating repels water and dirt), 2004 Cleaning w/polymer beads (90% water reduction), 2009 Cleaning w/green solvents and ionic liquids (no free water), 2011 Equipment patents exist already for consumer solvent cleaning!
Current Vision for Laundry Cleaning Target: Institutional markets now (hotels, hospitals, nursing homes, schools, military, prisons, etc.) Support from Customer Relationships(detergent manu) Form Strategic Alliances with “green” solvent manu Form Partnerships with equipment manufacturers (Anticipated) Cleaning Solvent Composition –Green Solvent> 90% –Water< 5% –Ionic liquid co-solvent(s) < 1% –Other additives (brighteners, fragrances, surfactants) < 4%
Current Vision for Laundry Cleaning “Green” solvent + detergent package (ILs) will clean ~ loads of laundry (based on density limits) with rinsing Cleaning solvent would be filtered/recovered; waste residue sent for disposal (after accumulation) Rinse solvent becomes cleaning solvent Add fresh (or recycled) solvent to rinse tank
Solvent Cleaning Benefits (1) Energy Efficient–Energy to heat solvent water; IL repels the solvent; no dryer expected! Water Efficient –no water is used; solvent will clean loads depending on contamination and density Cleaning Efficiency –recycling solvent means less added chemicals; fabrics will look/smell as if cleaned using water Environmentally safer –solvents are low/non-VOCs, non- hazardous, biodegradable, non-toxic Green
Solvent Cleaning Benefits (2) Softening andCleaning–ILs add softening, anti-static, cleaning, anti-bacterial(?), fragrance retention properties Recyclability–solvent used times with clean rinses Reclaimability–used solvents are recovered for future use Equal/Better Overall Cleaning Performance –contaminants are (1) filtered off and (2) part of distillation residues Closed-Loop Process
Waterless Cleaning must Work with Potential Customers in institutional laundry Form a Strategic Alliance with key solvent manufacturers Form Partnershipswith laundry equipment manufacturers Find Investors(angels, venture capitalists, banks, SBIR grants) Hire key personnel