Chapter 3

无机化学电子教案


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; andTo 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 toDecember 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

Industrialecology

Greenengineering

Greenchemistry

Renewableenergy

Practical approaches

Sustainabledevelopment

Strategic goal

Life-cycleassessment

Catalysis

Wastemanagement

E-factor,atom economy

Process intensification

Operational tools

Monitoring tools



Oxidation of diphenylmethanol to benzophenone

O

OH

3 + 2CrO3 + 3H2SO4

+ 2Cr2(SO4)3 + 6H2O

diphenyl methanol

benzophenone

stoichiometric reagents

waste

3



Relative efficiency of various engine types

% Efficiency

Gas electric

100

90

80

70

50

50

40

30

20

10

Diesel electric

Micro-turbine

Hydrogen fuel cell

Costs of obtaining hydrogen



The traditional propene oxide route

+ HOCl

propylene

OH

Cl + HClO

chlorohydrin propylene oxide

+ HCl + NaOHO + NaCl + H2OO



The SMPO process

O

t-butyl hydroperoxide

OOH+ OH+ OCH3

MTBE

Mo catalyst

+ CH2=CH2

Zeolite

+ O2OOH

+OOH

Ti/SiO2 O+

OH

OH

Alumina+ H2O

styrene

ethylbenzene hydroperoxide

ethylbenzene

Catalytic oxidation of propene



The four stages of life-cycle assessment

Life-cycleassessment

Definingthe scope

Inventory analysis

Impactanalysis

Improvementanalysis

Stage 1 Stage 2 Stage 3 Stage 4



Different types of catalysts

copper-zinc crystallites on silica

zeolite (crystalline aluminosilicate)enzyme (biocatalyst)

P P

OMe

OMe

(R,R)-DiPAMP-Rh (organometallic complex)

Rh

H B

F

FF

homogeneous acid catalysts

NH

CO2H

L-proline (organocatalyst)



Examples of chemo- and diastereoselectivity

+ CO + H2

C5H11

O

C5H11

O

+

Rh complex

nonanal iso-nonanal

+ O2

-pinene

CrCl3

-pinene oxide diastereomers

verbenone

O

O

O

+ +

N

MeO

+ H2

prochiral imine (R)-enantiomer

NH

MeO

NH

MeO

+

(S)-enantiomer

Ir complex * *

Regioselectivity

Enantioselectivity



Base-catalysed transesterification of triglycerides

O

OO

OH

OH

OH

O R1 OR2

O

R3

+ 3MeOH

OH–

catalyst

+ R2COOMe

R1COOMe

R3COOMe

triglycerides glycerol fatty acid methyl esters(FAME)

used as biodiesel



Green Solvents and Ionic Liquids

Waterless Cleaning LLC is100 % owned by Stan Seelig and Tony O’Lenick, with combined 60 years of industrial/consumer experience in cleaning/personal care.Mission StatementTo provide green/sustainable cleaning formulations using “green” solvents and ionic liquid co-solvents for the replacement of wasteful, water-based formulations and practices.Company Vision1.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 < $1/gm, others > $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 ~20-

40 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; spin drying

of solvent>water; IL repels the solvent; no dryer expected!

•Water Efficient –no water is used; solvent will clean 20-40

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 20-40 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

Documents

Chapter 3