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GCES User`s Manual

1. The SMART module performs checks to find most data entry errors For example assume that the amount of carbonic dichloride recovered in Sample 1 Figure 11 was originally entered as 1 000 kg per batch You can simulate this error using the Sample 1 data by double clicking on Data Entry Error A data entry or rounding error has occured The amount of Carbonic dichloride 000075 44 5 recovered is too high by e 21 5999 kg year 10 79995 kg batch Please edit the data for Carbonic dichloride and try again Figure 26 Error Message Screen Excess Chemical Recovered carbonic dichloride in the Chemical Summary Screen Figure 13 editing the amount recovered to read 1 000 kg selecting Continue and then selecting SMART Perform Assessment An error message shown in Figure 26 appears This message tells you where the data entry error likely occurred as well as the magnitude of the error Click on OK to go back to Chemical Summary Screen Figure 13 You can then review the data on the Chemical Information Screen Figure 15 for carbonic dichloride and correct the error In this case reducing the amount recovered by at 25 least 10 8 kg batch or increasing the amount of carbonic dichloride used in the reaction could eliminate the error Please note that the SMART module is an estimation tool and that the algorithm ignores errors less than one percent of the batch volume It is possible that your data will appear to be correct even tho
2. energy efficient reactions solventless reactions Searches may be narrowed by combining categories subcategories and other search terms with the search operators or and on the bottom of the window The search results if any will be displayed multiple search results are displayed in a table format As in the Green Synthetic Reactions module the search operators work only when combined across different search fields Further an asterisk may be used as a wild card to truncate the front or back of a search term or may be used alone in any field to return all of the references with entries in that section 42 Welcome to Green Chemistry References Module Figure 41 Green Chemistry References Main Screen Figure 42 Green Chemistry References Search Screen 43 The following sample screen provides an example of the results of a search for phosgene in the key words field Figure 43 You can browse the references using the navigation keys at the bottom of the screen You can choose to Perform Another Search or print the results by clicking on either the Print Entry or Print List button When you are finished and wish to exit this module click on File Close Module on the top menu bar or click on the Done button Green Chemistry References Search results Category Green Chemistry Subcategory general green chemistry references Author ie Paul T Williamson Tracy C a chemistry an overview Journal i Symp
3. by chemical characteristic This module is intended to be used as a tool for assessing relative toxicities of chemicals so that you may easily consider toxicity as a factor when choosing or designing chemicals for a process The current version of the GCES provides information on designing safer chemicals in a variety of classes and contains a limited number of examples of Designing Safer Chemicals More examples will be added in future versions You may check www epa gov greenchemistry for updates Welcome to the GCES Designing Safer Chemicals Module This module provides guidance on how safer chemical substances can be designed You can either search the reference section or look for information based on Chemical Class Chemical Characteristic or Chemical Use Search Examples Chemical Classes Chemical Characteristics Chemical Use Figure 32 Designing Safer Chemicals Main Screen 2 Using the Module From the main menu choose one of the section buttons In this version information is limited to chemical classes links to characteristic estimation software and some searchable examples Select the section of choice by clicking on it or by choosing the section from the Designing Safer Chemicals menu in the menu bar at the top of the screen 32 Selecting Chemical Classes will bring up screen that lists the major classes for which information is available Click on a topic to select it and open up a sub program that behaves like st
4. 88 3 for toluene to 108 38 3 for m xylene a prompt will appear Figure 28 when you click outside of the ID box Selecting Yes will look up the data for the new ID and overwrite the name molecular weight and SMILES notation Use this option if you want to change the chemical used in the reaction and replace it with another e g changing the toluene solvent in the Sample reaction to m xylene Select No if you simply want to change the chemical ID when for example an Other Unique Identifier was used initially and a CAS RN was 26 found later In this case the system will only change the chemical ID The ID has changed Overwrite X Select Yes to look up the chemical and overwrite existing data with the new Name MW and SMILES Select No to change the ID but not the Name MW or SMILES The quantity role quantity recovered and equivalents will not change as a result of this action Figure 28 Chemical ID Change Prompt Screen You may also correct the SMILES notation Make the necessary changes to the SMILES notation When you click in another box you will be prompted to confirm the change You can change the Name and MW in this manner but you will not be prompted for confirmation The quantity quantity recovered role and equivalents fields can be changed at any time After you return to the Chemical Summary Screen Figure 13 and select SMART Perform Assessment the results will reflect the changes you
5. Yes No If Yes proceed if No Go To 22 4 Halogens are absent from the polymer Yes No If Yes Go To 7 if No proceed 5 Halogens are only covalently bound to C Yes No If Yes Go To 7 No proceed 6 Halogens are only monatomic anions Cl Br or I and no fluoride anion F is present Yes No gt Figure 35 Designing Safer Polymers One Page Summary Screen The two possible outcomes of the analysis are 35 The polymer being manufactured is safer than many other polymers and may qualify for the polymer exemption from TSCA Section 5 reporting requirements for new chemicals If the polymer decomposes degrades or depolymerizes it may not qualify for the polymer exemption Further information regarding the Polymer Exemption Rule a Technical Guidance Manual for the exemption and the Chemistry Assistance Manual for Premanufacture Notices can be obtained from the TSCA Hotline at 202 554 1404 or The polymer does not qualify for the polymer exemption You may be able to develop a safer alternative that satisfies the conditions of the polymer exemption rule Use the guidelines in this module to identify an alternative that both retains its manufacturing specifications and meets the requirements of the polymer exemption As you progress through the algorithm whenever a yes no choice you have made produces a does not qualify result push the Back button and examine what disqualified the polymer from exemptio
6. charged formed the amount recovered and the amount of waste see Figure 23 If a chemical is not in the Lookup Table the system will not be able to provide information about EPA regulations In this case you will see a warning message and the check boxes for the regulatory lists will be grey For this screen and all the other output screens in the SMART module click on OK to close the screen and return to the previous screen ID VETE Role Feedstock Name Carbonic dichloride SMILES o CiCCI Molecular Weight 932 Regulated under EPCRA 302 X EPCRA 313 X CAA112 X HAPS X Batch Data Quantity kgs 4946 00 kmol 50 00 Equivalents Recovered kgs Percent Waste Annual Data Waste kgs Figure 23 Detail Screen gt To Use the Green Suggestions Button The Green Suggestions button on the SMART Assessment Summary Screen Figure 20 will become active when hazardous chemicals are used or formed in a chemical process For the current version of the GCES this button is activated when Tier 1 or Tier 2 chemicals are present If this button is active you may click on it to see the Green Suggestions Screen Figure 25 A ball and text appear directing you to other GCES modules After completing the SMART assessment check the suggested modules You may be able to find relevant information leading to a green alternative to your process reaction conditions or product 22 After you have com
7. combination of boiling point range melting point range and or a water solubility range Figure 39 If you enter more than one range the module will search for a solvent with properties in all the entered ranges The solvents are displayed with their full set of data Use the navigation arrows at the bottom of the screen to view the solvents matching the Search for solvent with BP between EE and je C and MP between ERN and ERES ve and Water Solubility between and mg Kg Figure 39 Physical Chemical Property Search Screen 39 search criteria You may print the data for the displayed solvent by clicking on the Print button Select Return to Previous Menu to return to the Green Solvents Reaction Conditions Main Screen You may also search in Browse Solvents Database Screen Figure 37 using the Microsoft Access search function If you are looking for a particular solvent you may use Search Search Database from the menu bar in the upper left corner This search method is useful when you are looking for a specific chemical by CAS RN or chemical name or part thereof Microsoft Access users will recognize this screen as the usual Access Find command Before selecting this menu item identify the search field by clicking in either the CAS RN or the chemical name field in the Browse Solvents Database Screen Figure 37 Thus if you click in the chemical name field and select Search Search Database from the menu the system
8. into the directory c gcesinst Once the extraction is complete you may delete gcesinst exe Run the setup program by selecting File Run from the Program Manager Windows 3 x or Start Run Windows 95 and entering c gcesinst setup exe in the command line box that appears The setup program creates the appropriate directories for you and copies the program files to your hard drive A copy of this manual can be found in c gcesinst manual pdf You may cancel the installation at any time but if you do so rerun the entire installation process to ensure all components are installed correctly You should not need to rerun the extraction process You will be asked to confirm the drive and directory where the files will be installed the default is c gces The final screen in the installation program will display the settings chosen and wait for your confirmation Figure 1 To continue installing the GCES click on the large computer icon The files will then be copied to the specified drive It is recommended that you install GCES on an internal hard drive You may load the system to a removable drive but performance may suffer because of slow data access times Green Chemistry Expert System Setup x Begin the installation by clicking the large button Complete Install all files for this application Directory CAGCES Figure 1 GCES System Setup Screen After the initial installation you will see the Installation Option
9. may narrow your search by combining terms with the search operators or and on the bottom of the screen Please note that these operators only work when combined between different search fields For example you may search for nitrile in the key word field and Smith in the reference field However you cannot search for Smith or Jones in the reference field An asterisk alone in any of the fields will return all of the records in the database Note that key words must match the wording in the citation exactly and thus you may obtain the best search results by keeping your search criteria as broad as possible You can use word fragments to broaden your search For example searching acet in the key word field will match acetyl acetic acetate and acetone 28 Enter your search term s for any or all of the following fields Pollution Prevention Comments Key word s Status Reference Search operator Or And Close Module Figure 30 Green Synthetic Reactions Search Screen The current version of the GCES utilizes a simple search engine that queries the entire database Sequential searches of intermediate record sets data subsets are not possible although you can obtain the required information by the careful selection of search terms Please note that superscripts and subscripts are not used in this module for example CH OH is represented as CH30H Searches in the Gr
10. reaction process the reaction identity or name Reaction ID the typical number of batches per year and the expected percent yield of the reaction You should also be prepared to provide the following information for each chemical used or formed in the process CAS Registry Number CAS RN if known the kg batch charged or formed the kg batch recovered the role of the chemical in the reaction e g feedstock product solvent etc and the number of equivalents required or formed this information is not needed for catalysts solvents impurities and byproducts Use a CAS RN if you know it The GCES includes a Lookup Table with basic information on over 60 000 chemicals listed by CAS RN note this list is not reflective of TSCA inventory Ifthe CAS RN you enter is in the database the GCES automatically looks up the chemical name the molecular weight and the SMILES notation 1 e the chemical structure If a chemical in the manufacturing process does not have a CAS RN you will also need to enter a unique alphanumeric identifier for the chemical so that the system can store information on this chemical for your use later The SMART module uses Simplified Molecular Input Line Entry System SMILES notation to represent molecular structures by strings of symbols Discussion of SMILES notation is outside of the scope of this document You should consult Weininger s original paper on thi
11. the reaction Perhaps this can be limited to stoichiometric amounts This would 24 be true if a replacement for phosgene could be found eliminating the need for consuming HCl When you have finished viewing all of the information click on OK until you return to the Chemical Summary Screen Figure 13 At this point you can save this chemical process if you have not already done so and then make changes to the input data to test one or more scenarios to reduce the amount of waste in the reaction The SMART module thus offers you an opportunity to identify some of the environmental concerns directly associated with the manufacturing process for a specific chemical product There are however other environmental concerns that are not at all addressed by the SMART process because they are indirect results of the manufacturing process For example a clean process that requires significant heating supplied by a large oil burner may not be free of environmental concerns even if the chemistry of the reaction is benign Using the SMART module and any knowledge that you may have about indirect environmental effects you can quickly evaluate a variety of alternative chemical processes and compare the results against the original process This allows you to identify a process with less environmental impact The SMART module can therefore be used as an effective tool for evaluating cleaner chemical processes 5 Additional Information Error Messages
12. 3 Viewing the Search Results 22 2 cis lr s kg pua ok y pi Rx 30 C Designing Safer Chemicals oooooooooooooooororr9rrrroroos 32 1 Description of the Module sseleeeeeee eee 32 2 Usme the Module occitano AE AAA 32 3 Example Nitrile pci pue o A E a ed a 33 d Example Polymers issc aia o etana pip pdou Ceca s PIC roti 34 5 Chemical Characteristics Linking Estimation Software 36 Green Solvents Reaction Conditions lees 37 1 Description of the Module 52e IIb Er RR RI 37 2 Using the Module sr elas 37 3 Searching the Solvent Database socios 39 Green Chemistry References sssssssoosessoocesssoceessooe 42 1 Description of the Module vicio a dios 42 2 S arching th Modules gata pb dos pb ds 42 3 Addme R ferences pr A AAA A 44 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 List of Figures GCES System Setup Screen sii ad DARE DEAE DESDE LAE ES 3 Installation Options Screen 6 04 02 2905 05 83 5S ee 8 Re en TOR EP SCARE ERAS 4 OCES Startup Scree e prster petu let eoe lepex vete lace s ede hea end 5 GCES Mam Menu Screen 22x22 9 RAS WEE ooh EXER TELA 6 Preferences SCIES cu salue iux ad iua A ERES IQ Wax Eg xd 6 GCES Help Screen ri IA pate eda ee ee pee eae es ae eek 7 SMART Mern Screen co dde dla raten BH ale Race E nee OM ak sien Rates 10 About the SMART Assessment Screen ooooooooconroororranr ee eee 11 Reaction Information Scre
13. 9 892 CAS Chemical fRole Waste Waste Kes 000075 44 5 Carbonic dichloride Feedstock 1522 197840 Yes Total Waste 15 22 ees 1978 40 kes Figure 21 Tier 1 Summary Screen gt To View the Total Waste Summary To view this summary click on the Total button on the SMART Assessment Summary screen The Total Waste Screen appears in Figure 22 It includes all the chemicals in the reaction Reaction Summary ld Sample 1 nmal Production Volume kgs 13 000 Feedstock 000080 05 7 Phenol 4 4 1 methylethylic Feedstock 000075 44 5 Carbonic dichloride Feedstock Product Product Product 007647 01 0 Hydrochloric acid Coproduct y 5833 60 Total Waste 132 60 17238 00 kgs Figure 22 Total Waste Summary Screen 21 including Tier 4 gt To View the EPA Regulated Chemicals in the Reaction Click on EPA Regulated to view a list of all the chemicals in the reaction that are regulated under the lists mentioned above EPCRA sections 302 and 313 Clean Air Act section 112 r and the Hazardous Air Pollutants If there are no chemicals from these lists in the reaction this button will appear grey and be inactive The screen looks similar to the summaries shown in Figures 21 and 22 gt For more information about any chemical For more information on a particular chemical either double click on the chemical of interest or select it and click on Details from a summary screen A new screen will be displayed summarizing the amounts
14. ART 1 Description of the Module Since 1993 the SMART assessment has been part of the Agency s review of Premanufacture Notifications PMNs received under the Toxic Substances Control Act TSCA The program was initiated by the Agency to alert PMN submitters to possibilities for reducing or eliminating the use or generation of hazardous substances during the manufacture of new chemicals i e to identify and pass on opportunities for pollution source reduction It is the Agency s hope that the non regulatory voluntary suggestions made by Agency chemists will encourage chemical manufacturers to review their manufacturing processes and reduce the hazardous materials related to these processes The primary purpose of the SMART module is to help chemical manufacturers understand how the Agency performs its internal SMART reviews and to make this tool available so that manufacturers can perform similar analyses during the course of chemical and process research and development prior to filing a PMN with the Agency The SMART assessment techniques are however applicable to both new and existing substances Secondary purposes of the system include helping manufacturers of existing chemicals to identify and reduce the use and production of hazardous materials and supporting academic institutions in the training of chemists in source reduction The source reduction opportunities identified by the SMART module may include such things as the need to
15. Branch 7406 U S Environmental Protection Agency Office of Pollution Prevention and Toxics 401 MSt SW Washington DC 20460 Telephone 202 260 2659 Fax 202 260 0816 or 202 260 0981 E mail farris carol epa gov or fritz greg epa gov DISCLAIMER The Green Chemistry Expert System is part of EPA s Green Chemistry Program a voluntary pollution prevention initiative that promotes the research development and implementation of green chemistry technologies The System is a software package designed to provide users with information and tools to make new or existing manufacturing processes less hazardous to human health and the environment Use of the GCES does not exempt the user from any regulatory responsibilities The GCES should not be used for reporting or other regulatory activities Il SYSTEM REQUIREMENTS The GCES is designed for use with Microsoft Windows version 3 1 or higher It requires a color monitor and the capability of displaying a minimum of 16 colors The GCES must be run on a drive for which you have write permission and requires approximately 20 megabytes of disk space for complete installation although it can be installed with as little as 5 megabytes using the minimal installation option The minimal installation option requires an additional 15 megabytes on another disk such as a removable media drive for the external databases You do not need write permission for this space It is recommended that you
16. RA and TSCA hotlines The EPCRA Hotline number is 800 424 9346 or 703 412 9810 in the Washington DC area the TSCA Assistance Information Service number is 202 554 1404 and its E mail address is tscahotline epa gov Tier 3 Total waste for Tier 3 chemicals Tier 3 includes all chemicals of unknown or intermediate toxicity This is a broad category that includes those chemicals not included in Tiers 1 2 or 4 Waste 1 2 3 Total hazardous waste This is the sum of all of the hazardous or potentially hazardous waste Tiers 1 through 3 Tier 4 Total waste for Tier 4 chemicals Tier 4 chemicals are a few relatively innocuous compounds that pose little or no risk of harm under normal usage conditions Examples are water sodium chloride and nitrogen The percent of waste generated in each tier relative to the production volume is shown to the right of the tier buttons on the summary screen gt To Print SMART Summary Data Click on the Print button gt To View the List of Chemicals in Each Tier To view the list of the chemicals for the present reaction that are in each tier click on the button for that tier In the example above there is no Tier 3 or Tier 4 waste and therefore the buttons appear grey and are inactive As an example the Tier 1 Summary Screen for Sample 1 appears in Figure 21 20 Tier 1 Summary ld Sample 1 Anmal Production Volume kgs 13 000 Tier l total anrmal amount charged or produced
17. Ser Volume 626 Pages fi 17 Date fi 1 96 Abstract review with 72 refs of the Green Chem movement in the chem industry and its effect on research and potential industrial manufg processes The Green Chem movement is an approach to the synthesis processing and use nf chems that reduces risks tn humans and the enviranment and nan E b Lal Figure 43 Green Chemistry References Search Results Screen 3 Adding References You may add your own references to this module by selecting Add Delete References from the Green Chemistry References Main Screen Figure 41 A screen appears allowing you access to the user entered portion of this database Figure 44 Any references previously entered will appear here You may browse and edit these records Click on Add New Record to add a new blank reference Simply fill in the information for your reference Be as complete as possible to facilitate future searching Click on Delete This Record to delete the currently displayed reference Browse through the records using the navigator buttons at the bottom of the screen References added in this portion of the database are automatically searched during any search of the References module 44 Add Delete References Figure 44 Add Delete Reference Screen 45
18. The information supplied for each chemical includes when available see Figure 38 molecular weight boiling point melting point specific gravity vapor pressure water solubility log octanol water partition coefficient Henry s Law constant flash point explosion limits dielectric constant ozone depletion potential global warming potential more information on global warming potential is available by clicking on the About GWP button and EPA Regulations more information about these lists is available by clicking on the About EPA Regs button 38 000057 55 6 Propylene glycol Molecular Weight 76 11 Water Solubility mg kg 1000000 Boiling Point C 188 2 Dielectric Constant B2 Melting Point C 60 log OctanoliWater Partition Coefficient 0 92 Specific Gravity 1 033 Vapor Pressure mm Hg 0 133 ps C FlashPoint C 98 88 Henry s Law Constant atm cu m mole 1 74E 07 Explosion Limits 2 6 12 6 RTECS TY2000000 Ozone Depletion Potential Global Warming Potential EPA Regulations HAPS EPCRA 302 EPCRA 313 CAA 112 r About EPA Regs About GWP Figure 38 Physiochemical Properties Screen After reviewing the data click on OK to return to the list of solvents 3 Searching the Solvent Database After selecting Search Solvents by Physiochemical Properties from the Solvent Database Main Screen enter any
19. User s Manual Green Chemistry Expert System GCES Version 0 99 Industrial Chemistry Branch Economics Exposure and Technology Division Office of Pollution Prevention and Toxics U S Environmental Protection Agency 401 M Street SW 7406 Washington DC 20460 Developed under contract by Environmental Science Center Syracuse Research Corporation 6225 Running Ridge Road North Syracuse NY 13212 Table of Contents Table of Contents sana A AA AAA i List of FIQUPOS 95 5 SANO iii L INTRODUCTION S eee ax mer qr a SER ER SI 1 Il SYSTEM REQUIREMENTS ooooooocoocorcorcoocoocooccosrosooo 2 BlL AINSTALLATION 553 Sie RR PR n Roe ROA baad E SACR e CR 3 IV STARTING THE GOES 9533 65 05 ce 53 08 EAS RAR ARR E RAE RETO EE 5 Pr ferences MEU over Ch SRI OR sn a LU IC 6 V RUNNING HELP IN THE GCES oooooooocoooccocrcocrcomcommoooo 7 VI RUNNING THE GCES MODULES o ooooooooooocoocoooooooos 8 A Synthetic Methodology Assessment for Reduction Techniques SMART 8 1 Description of the Module 24 292 irrita paras 8 2 Starting the SMART MOqule AA AA 10 3 Entering Reaction Data 2 ir e EL LESE CR Es 12 4 Running the SMART Assessment 0 0 00 eee eee ee eee 19 5 Additional Information Error Messages 0000s eee eee 25 B Green Synthetic Reactions ccc ccc cece ec ccc cece eee nnn 28 1 Description of the Module 0 0 eee eee 28 2 oearehime the Modules is iaceo ds 28
20. akes you back to the Reaction Information Screen Figure 9 where you may change the yield and number of batches for your reaction gt To Edit or Delete an Entry for a Chemical Substance in the Lookup Table To edit or delete the information for any chemical stored in user section of the Lookup Table select Maintenance Edit or Delete Record from Userlist on the top menu bar then choose the desired chemical from the drop down menu see Figure 18 4 Running the SMART Assessment After you have entered all the information about the reaction and its related substances you may perform the SMART Assessment To perform the SMART assessment on the chemical process select SMART Perform Assessment on the top menu bar or click on the SMART Review button The program will perform a series of mass balance calculations and will provide you with the waste amount and hazard classification for each chemical used or formed in the process The system will also provide summaries by hazard class and a qualitative level of concern The SMART Assessment Summary Screen Figure 20 shows the total amounts of materials calculated in each of the hazard tier categories as a percentage of annual production volume SMART Assessment Summary Waste as a Percent of Production olume 15 22 Tier 1 Tier2 Tier 2 117 38 Tier 3 Tier 3 0 00 Waste 1 2 3 Total 132 60 Tier 4 Tier 4 0 00 Product Product Volume 1 30E 04 5000 10000 15000 20000 kg year Level of Con
21. and related fields To proceed with a search click on the Search References button Figure 41 The search function of this module is similar to that used in the Green Synthetic Reactions module You may want to refer to Section VI B of this manual for detailed instructions on its use 2 Searching the Module You may browse the database by category and subcategory Select a category of interest with or without a subcategory in the Green Chemistry References Search Screen Figure 42 and click on Perform Search To perform a search for specific information enter information in any of the fields Author Title Journal or Key word Note that at present you cannot search by date or volume number Some key word suggestions include but are not limited to green feedstocks green chemical processing biomass separations renewable feedstocks extractions purifications green reagents analysis photochemical reagents process analytical chemistry hazardous chemical reduction elimination bioprocessing reduced solvent solventless processes waste reduction elimination energy efficient processes green chemical synthesis manufacturing catalysis biocatalysis atom economy green solvents aqueous conditions derivatized polymeric solvents ionic liquids supercritical solvents designing safer chemicals inherently safer chemicals less toxic chemicals biodegradable chemicals green reaction conditions J less persistent chemicals
22. andard Windows on line help Within this sub program you have a number of options available for navigating and printing the class specific information You can print a topic screen by choosing the Print button or File Print Topic from the menu bar at the top of the text screen To re read a previous screen you may click on the Back button Depending on how many times the Back button is pushed this function will bring you all the way back to the initial screen for the topic you chose under a specific chemical class In addition you may view a history of the pages you have visited by choosing the History button from the top menu bar Windows 95 users should select Options Display History Window Double clicking on any title listed in the history will bring up that page You can also access information on the other topics within the chemical class by clicking on the Contents button To return to the GCES Main Screen close the sub program by selecting Exit from the File menu Alternatively you may use any of the standard Windows short cuts The Chemical Characteristics section of Designing Safer Chemicals has links to other software that allow you to estimate some of the characteristics of chemicals See section 5 below for more information on using these links 3 Example Nitriles Choosing nitriles from the list of chemical classes brings up the Nitriles Screen Figure 33 You may review any of the listed topics by clicking on the correspo
23. arch Results Screen o ooooooooooooo oo 31 Designing Safer Chemicals Main Screen 0 0 0 e eee ee eee 32 Nitrles Main Screen zi ii eee ee E WES 33 Polymers Maln Sereen 3 cies kx eoe A E ENE E Stet 34 Designing Safer Polymers One Page Summary Screen 35 Green Solvents Reaction Conditions Main Screen ooo oooocoooocoooooo o 37 Browse Solvents Database Screen ara a as a a Pee 38 Physicochemical Properties Screen 0 0 0 eee eee eee 39 Physical Chemical Property Search Screen 0 0 0 0 eee eee eee 39 Microsoft Access Search Screen 0 00 cece ccc eee teens 40 Green Chemistry References Main Screen 00 00 e eee eee eee 43 Green Chemistry References Search Screen 0 00 e eee eee ees 43 Green Chemistry References Search Results Screen oo oooooooooo 44 Add Delete References Screen c evisos parta ires aeg ree uec ss 45 iv I INTRODUCTION The Green Chemistry Expert System GCES was designed to be used to identify opportunities to eliminate or reduce the use of hazardous chemicals and the production of hazardous waste The GCES is comprised of five modules Synthetic Methodology Assessment for Reduction Techniques SMART a program designed to quantify and categorize hazardous material used or generated as the result of a manufacturing process Green Synthetic Reactions a searchable database of synthetic processes that identify alternative pr
24. breviation trade name notebook page R amp D code etc may be used as a Unique Identifier name If this same Unique Identifier has been previously entered into the system and saved in the Lookup Table the system will retrieve the molecular weight chemical name and SMILES for you If you have forgotten a Unique Identifier you used previously you can find it in the Userlist of Chemical Identifiers Figure 18 Select Edit or Delete Record from Userlist from the Maintenance menu and using the pull down list by the entry box Choose the Chemical ID BH 000050 11 3 EXP 1 DeleteEntry Figure 18 Userlist of Chemical Identifiers Screen 17 For more information and descriptions of the data that you need to enter click on the at any time you are using this screen or select Help from the Help menu and read the information under the topic Substance Data Entry Edit See Section V above for more information on the GCES Help function If the chemical added is new to the database you will prompted to identify its category Figure 19 This helps the GCES classify the substance in the proper tier Form Category Form Figure 19 Chemical Category Screen When you have entered all of the data for the first chemical on the Chemical Information Screen Figure 15 select Continue and you will return to the Chemical Information Summary screen Figure 13 where you will be able to add edit or delete chemicals and their asso
25. ce Sheldon May The search results will be displayed on a form on the screen Click on the Print button if you wish to print the entire list of matches You can view each record in the query results by clicking on the outside arrow keys at the bottom of the screen to take you to the top E or bottom P of the list or clicking on the inside arrow keys to take you up 1 or down Pl the list one record at a time If it appears that the text does not fit in one of the text boxes simply double clicking in that text box will allow you to read all of the text contained inside An example of a search using phosgene is shown in Figure 31 The GCES had twenty five citations that met the search criteria You may print either the record shown or the entire list using the Print Entry or Print List buttons 30 Green Synthetic Reactions Search Results i 29 Alienative Yes Conventional No 1 CA 109 231707 Y agn T et al Marnfacture of isocyanates without phosgene PCT Int Appl 1988 Japan patent to Daicel Chemical Industries WO RR SA C A1 RRANTZIA A CA 121 301 575 du Ed process to diisocyanate Dimethyl carbonate DMC P2 Commenis Conventional route uses phosgene and generate HCl This process is a phosgene free process Status R amp D Patent WO 8805430 A1 880728 Vendor Daicel Chemical Industries Ltd Close Module I 14 4 Record 1 Figure 31 Green Synthetic Reactions Search Results Screen When y
26. cern EPA Regulated Figure 20 SMART Assessment Summary Screen 19 Product Production volume of the product chemical This represents the amount of chemical produced and isolated as useful product as entered on the reaction ID screen This is not a waste total Tier 1 Total waste for Tier 1 chemicals Tier 1 chemicals are a small set of chemicals that are exceptionally hazardous therefore their use or generation should be avoided if at all possible Examples are dioxins and phosgene carbonic dichloride Tier 2 Total waste for Tier 2 chemicals Tier 2 includes the chemicals on the Emergency Planning and Community Right to Know Act EPCRA sections 302 Extremely Hazardous Substances and 313 Toxics Release Inventory or TRI lists as well as the Clean Air Act section 112 r and Hazardous Air Pollutants lists In this manual EPA regulated chemicals refers to these lists only In addition it includes chemicals having functional groups associated with high toxicity e g acid chlorides alkoxysilanes epoxides or isocyanates that are derived from the OPPT internal list of chemicals of potential concern Some of the OPPT Chemical Categories are very broad As a result not all chemicals that are in an OPPT Chemical Category are especially toxic but they are screened carefully by Agency scientists as members of a Category during new chemical review Further information and copies of these lists may be obtained from the EPC
27. ciated data Click on Entry Add to add the next chemical substance You may edit a chemical entry by selecting the chemical or by highlighting the chemical with the mouse or the arrow keys on the keyboard and then clicking on Entry Edit You may delete entries by highlighting the chemical and then clicking on Entry Delete Continue this procedure until you have entered all of the chemicals in the process Check to see that you have entered all chemicals including feedstocks products solvents etc The analysis will not be complete unless all chemicals are added even non reactants There are a number of other commands available to you while you are using the Chemical Summary Screen Figure 13 In addition these functions are available on the Reaction Information Screen Figure 9 gt To Save the Reaction Data To save the reaction data click on Save or Save As from the File menu bar at the upper left corner of the screen gt To Print the Reaction Data To print the reaction data select on Print from the File menu bar gt To Open a Previously Stored Reaction To open a reaction saved earlier including the Sample reactions supplied with the system select File Open from the File menu bar or click on the Open Saved Reaction button on the 18 Reaction Information screen gt To Edit Reaction Data To edit reaction data click on the Edit Reaction Data button at the bottom of the Chemical Summary Screen Figure 13 This button t
28. e Polymer Exemption Rule provides detailed discussions on new polymers that are subject to full PMN review i e are excluded from the polymer exemption rule to PMN reporting because of their potential for adverse effects The Eligibility Criteria for Polymers not Specifically Excluded discusses the three classes of polymers eligible for a polymer exemption filing 34 those with a number average molecular weight greater than or equal to 1 000 daltons and less than 10 000 daltons low reactivity and low oligomeric content designated el polymers by the exemption rule those with a number average molecular weight greater than 10 000 daltons and lower oligomeric content designated e2 polymers and polyesters made from specified feedstocks designated e3 polymers Designing Safer Polymers leads you through an algorithm to determine whether a polymer is eligible for the polymer exemption rule and to determine the relative toxicity of a polymer based on its composition and physicochemical properties You can also view the entire algorithm on a single page Figure 35 amp Designing Safer Chemicals Polymers Iof xi File Edit Bookmark Options Help Cover 7 Bock Ein Safer polymer algorithm 1 The polymer is cationic or potentially cation Yes No If Yes proceed if No Go To 3 2 The combined cationic FGEW is 2 5 000 Yes No Yes proceed f No Go To 22 3 Of C H N O S and S1 two elements are integral
29. een Synthetic Reactions module may include but are not limited to some of the common terms for selected fields provided below Key words acid catalyst oxidation alcohol catalytic phosgene free amide chloride process amidocarbonylation chlorine free 1 3 propanediol amine DMC rearrangement anhydride enzymatic styrene aromatic hydrolysis supercritical bromination isocyanate THF carbon dioxide methyl urethanes carbonylation NMP water Pollution Prevention Comments acetic alkyl aromatic acetone alternative arylation acid amine bromination alcohols ammonium byproduct aldehyde anhydride carbon 29 carbonylation catalysis catalyst CH30H chlorine Cl concern conditions convenient conventional coproduct DMC eliminate ethylene feedstock formation HCl HCN HF Status commercial commercially lab new HNO3 H2S04 hypochlorite inexpensive intermediate isocyanate ketones liquid nitration non acidic non toxic oxidation phosgene process produce propylene pure reaction reacts reagents patent pilot plant produce recycled removed route safety salt SC CO2 secondary sodium solvent source styrene sulfate sulfuric supercritical system traditional waste water yield production R amp D scale U S Reference Note that titles of articles are included but that not all articles actually have titles 1992 Encyclopedia Joseph 3 Viewing the Search Results market News Scien
30. emical that is expected and necessarily generated as a result of the synthesis of the desired product For example the production of methanol in the hydrolysis of a methyl ester Byproduct any chemical that is unexpectedly formed in addition to and usually at the expense of the desired product For example production of a diester from a diacid and an alcohol when the desired product is the mono ester Note This definition of a byproduct differs from the definition in the PMN rules 40 CFR 720 3d 1990 Byproduct means a chemical substance produced without separate commercial intent during the manufacture processing use or disposal of another chemical substance or mixture The definition used in the PMN rules could include both coproducts and byproducts as defined for the GCES For products and coproducts you may select autocalc instead of providing a quantity formed When autocalc is active the SMART module will calculate the amount of the substance formed during the reaction using the yield that was entered in the Reaction Information Screen Figure 9 It is strongly recommended that you use autocalc for coproducts It is also a useful feature if you only know how much product is recovered from the reaction and not how much is formed If the CAS RN is not found in the Lookup Table or you do not provide a CAS RN you will get a message that the substance was not found in the Lookup Table and you will be asked if you w
31. emicals Program assesses risks that may be posed by the new chemical substance itself e SMART Program reviews the complete manufacturing process used in making the new chemical looking at SMART Tutorial ms Figure 8 About the SMART Assessment Screen 11 3 Entering Reaction Data To perform a SMART assessment on a new or saved chemical reaction read the disclaimer and choose I understand proceed to SMART Assessment from the SMART Menu Screen Figure 7 You must then enter basic reaction information either by typing it into the system for a new assessment or by calling it up from the program memory for a saved assessment To begin a new assessment you must enter a unique name in the Reaction ID field and provide the following process information number of batches year and percent product yield i e actual total mass of product formed theoretical maximum amount of expected product x 100 If you only know the percentage of product recovered enter that percentage for the reaction yield When you are finished click on the Continue button at the bottom of the screen see Figure 9 To perform a new SMART Reaction ID assessment please provide the reaction data then click continue Batches year to add the chemical specific information Reaction Yield 14 Figure 9 Reaction Information Screen To call up a saved reaction click the Open Saved Reaction button or pull down the File menu and select O
32. en ute sat wstex a Deu 12 Open Saved Reaction Screen Mad rd usu EE e e eue 12 Sample 1 Chemical Reaction and Associated Data lille 13 Reaction Information Screen Samplel 0 0 eee eee eee 14 Chemical Summary Screen osea Soh nhs DARIA sd aes 14 Chemical Identification Screen 4 Lucca vus prose luda vat eru ace ora 15 Chemical Information Screen 241i goo ee eee eee ee 15 CAS Registry Number Not Found Screen 0 0 0 eee eee eee eee 16 Chemical Information Screen for Data Entry 0 0 0 0 ce eee eee 17 Userlist of Chemical Identifiers Screen 1 0 0 eee eee eee 17 Chemical Category SEO Roe I x i AC e e LR e el AES 18 SMART Assessment Summary Screen 0 000 cece ee eens 19 Tier Summary Screen verbe e al i eus de a es 21 Total Waste Summary Screen muii ii a CR AU be eh es 21 Detail Screen 2 05 SR oA S UA SORERD UN ened ihe one aras 22 Green Suggestions Screen e pala bd Bee QU qd gn 23 25 26 27 28 29 30 31 22 33 34 35 36 37 38 39 40 41 42 43 44 Level of Concern Screen ses ote EE A EA AA A et 23 Error Message Excess Chemical Recovered Screen o ooooooooooooo oo 25 Error Message Yield gt 100 Screen 26 Chemical ID Change Prompt Screen 0 0 eee eee eee 27 Green Synthetic Reactions Main Screen 0 0 cee eee ee eee 28 Green Synthetic Reactions Search Screen 0 0 0 e eee eee eee 29 Green Synthetic Reactions Se
33. f the list towards the last record the Up setting can be used to re find a previous record Match Case This check box indicates 1f the search will be match upper and 40 lower cases when checked or not Search Fields as Formatted Select this option to find data based on its display format Find First Use this to find the first occurrence of the text string in the database Find Next Use this function to find the next occurrence relative to the cursor you may repeat this function until the last occurrence of the text string is reached and Close This button closes the Find feature and leaves the cursor on the selected solvent Sometimes matches are found but the highlighted text is hidden behind the Search Screen In this case simply click on the blue bar at the top of the Search Screen and drag it out of the way If you get no hits for your search check to be sure you searched in the correct field After completing a search click on Close to exit the search screen When you are finished viewing or printing the data in the Solvent Database module select File Close Form or the Close Form button from the menu to return to the module s opening screen Selecting the Return to Main Screen button or File Close Module menu item will return you to the main screen of the GCES 41 E Green Chemistry References 1 Description of the Module This module includes references to material published in green chemistry
34. have at least 8 megabytes of RAM available on your computer otherwise some parts of the GCES may be sluggish A mouse is required for ease of use of the system Using the system with minimal installation requires that the drive to which the external databases were installed be present In addition installation of the GCES requires an additional 20 megabytes of disk space Once installation is complete this space can be freed up by deleting the installation files The GCES is not designed for network use III INSTALLATION The GCES was developed using Microsoft Access version 2 0 a relational database management system developed by Microsoft Corporation Copyright O 1994 The GCES is operated using the Runtime version of Access a stand alone version of the program designed to perform custom applications developed using Access Microsoft Access Runtime is installed on your computer with the same installation disk as the GCES application software and is provided to you for the exclusive purpose of running the GCES Microsoft Corporation reserves all copyright protection of Access Runtime worldwide The current version of the GCES is provided for download from EPA s Green Chemistry web site http www epa gov greenchemistry After downloading locate the self extracting archive file gcesinst exe on your hard drive using the Program Manager or Windows Explorer and double click on it This will extract the setup files needed to install the GCES
35. identify benign chemicals as replacements for hazardous starting materials or the goal of changing a synthesis to prevent the formation of hazardous or unusable byproducts or coproducts In addition a search for green reaction conditions may be suggested to eliminate the use of hazardous solvents or improve the efficiency of the reaction thereby increasing conversion of feedstocks and reagents and increasing product yield and atom economy Successful source reduction strategies benefit the environment by reducing the amount of harmful and potentially harmful chemical wastes that may be released and may benefit the manufacturer through potential savings through reductions of starting materials and waste disposal The SMART module however only examines the chemicals directly involved in the manufacturing process of a commercial product There are other potential environmental concerns that are not considered by the SMART assessment for example the use of an oil burner to heat a chemical reaction even a green reaction may give rise to other pollution that is not addressed by the SMART module It is important to note that the GCES is a tool It cannot judge the relative merits of processes It can aid you in identifying some of the potential problems associated with a reaction and potential alternatives It requires that you make a reasoned judgement about the relative merits of the approaches found An alternative may still trigger concerns even th
36. indow is on the screen you can choose the Continue button from that window or you can click on File in the top left corner and select Continue from the File menu After you select Continue the GCES main menu will appear with the list of available program modules Figure 4 Select the module you wish to use from this list or from the top menu bar under Module Each of these modules is described in Section VI of this manual To exit the GCES return either to the GCES Startup Screen Figure 3 or the GCES Main Menu Screen Figure 4 and then select File Exit from the menu You will be prompted to confirm that you want to exit the GCES application You may also click on the Exit button on the Startup Screen but you will not be prompted for confirmation Welcome to EPA s Green Chemistry Expert System Figure 4 GCES Main Menu Screen Preferences Menu The preferences should be automatically set during installation However if you install components later on or if you move components you may need to change the preferences by selecting Preferences from the File menu The preferences screen will come up Figure 5 The IS Path for external tables c gces Path for bcfwin exe gg 005050 0 5 5 5 5 5 1 Path for biowin exe fc est Path for ecowin exe fe est Figure 5 Preferences Screen first entry Path for external tables is the directory where the two external data tables lookup mdb and greenref mdb a
37. iptions in this section have two hyper links to related subjects in the Guidance for designing safer nitriles section to enable you to recognize and avoid nitriles that are known to cause acute lethality or osteolathyrism It also suggests how to design nitriles that are less toxic The Guidance for designing safer nitriles button brings up a text screen describing structural modifications that are expected to reduce nitrile toxicity You may access other pages within this sub program by clicking on the green text highlighted with underlines 4 Example Polymers The polymers sub program was designed to highlight those chemical characteristics common to polymers that may pose an unreasonable risk to human health or the environment You may view any of the listed topics on the Polymers Screen Figure 34 by clicking on the corresponding button Polymers Polymers Excluded from the Polymer Exemption Rule Eligibility Criteria for Polymers not Specifically Excluded Designing Safer Polymers Figure 34 Polymers Screen The Introduction contains a brief discussion of how EPA reviews polymers under section 5 of TSCA Toxic Substances Control Act under section 5 the Agency reviews Premanufacture Notifications PMNs for New Chemical Substances Note that although much of the information in this module is derived from the Agency s review of new polymers the information is applicable to both new and existing polymers Polymers excluded from th
38. l be given a choice of reading about green solvents and reaction conditions searching by physical and chemical properties browsing the solvents database searching examples or returning to the GCES main menu Figure 36 Clicking on Green Solvents Reaction Conditions will bring up a list of alternative solvent systems Click on any of the entries in the list to learn more about each topic This portion of the module functions similarly to the chemical classes in the Designing Safer Chemicals module If you click on Browse Solvents Database 37 you will see a screen containing the list of all of the solvents in the database in CAS RN order Figure 37 To scroll through the list of solvents use the navigation arrow keys at the bottom of the list of chemicals to take you to the top ue or bottom of the list and the inside arrow keys to take you up Ld or down b the list one chemical at a time To view the available data for a particular chemical select the chemical by double clicking on it in either the CAS RN or name field or by selecting a record and choosing the View Data button See section 3 below for more information on how to search by CAS RN or name Mbooos0 00 0 000064 18 6 nnpnaa19 Acaticacid Record o5 2 View Data Return to Previous Menu i ES z E Ex p fe KI Figure 37 Browse Solvents Database Screen
39. made 27 B Green Synthetic Reactions 1 Description of the Module The Green Synthetic Reactions module is a database containing current references related to selected synthetic processes In the current version of the GCES this module contains only limited references it is planned for expansion in future versions The processes in the Green Synthetic Reactions module have been chosen as examples of green chemistry alternatives to replace conventional industrial syntheses The user can search the database in any of the following fields pollution prevention comments e g safety or inexpensive key word s status e g lab scale pilot plant or patent or reference Results are presented on a form that contains the full reference citation s a description of the reaction vendors the status and comments on the advantages of using each process for pollution prevention Welcome to the GCES Green Synthetic Reactions Module This module provides information on greener synthetic methods Return to Main Menu Figure 29 Green Synthetic Reactions Main Screen 2 Searching the Module When you choose the Green Synthetic Reactions module from the main menu you will be given the choice Figure 29 to search the database or return to the Main Screen If you choose Search the Database you will see the Green Synthetic Reactions Search Screen Figure 30 Simply enter the appropriate search specifications and click on Perform Search You
40. mistry Expert System iof x File Edit Bookmark Options Help Green Chemistry Expert System The Green Chemistry Expert System consists of several modules covering different aspects of environmentally friendly chemistry To choose a module click on the corresponding button on the screen Synthetic Methodology Assessment for Reduction Technologies SMART This module contains a program designed to assess the environmental impact of a given process This program calculates and categorizes the wastes generated in a process and indicates the Environmental Protection Agency s level of concern arising from the results Green Synthetic Reactions The Green Synthetic Reactions module 1s a database containing examples of selected synthetic processes These processes have been chosen as examples of green chemistry alternatives to replace standard industrial syntheses The user can search the database by pollution prevention comments e g safety inexpensive key word s status e g lab scale pilot plant patent or reference Results are presented on a form that contains the full reference citation s a description of the reaction the status and comments on the pollution prevention advantages for each process To retrieve all the examples enter an asterix in the reference field Din nt ete ce On Fane h natal Figure 6 GCES Help Screen 7 VL RUNNING THE GCES MODULES A Synthetic Methodology Assessment for Reduction Techniques SM
41. n The other Chemical Classes are set up in a similar format To exit the Designing Safer Chemicals module and return to the GCES Main Screen click on File Close Module 5 Chemical Characteristics Linking Estimation Software If you have EPA estimation software for bioaccumulation bcfwin biodegradation biowin or aquatic toxicity ecowin you may link the GCES to these programs to simplify your work in developing a safer chemical Select Preferences from the File menu Fill in the paths for any or all of the tools that are installed on your computer You may then launch the tools from the Chemical Characteristics section of the Designing Safer Chemicals Module by clicking on the appropriate button These programs are available from the EPA directly at the addresses below or from Syracuse Research Corporation esc syrres com esc 1 estsoft htm Questions about these products should be directed to Ecowin Vince Nabholz New Chemicals Screening and Assessment Branch 7403 US Environmental Protection Agency 401 M St SW Washington DC 20460 nabholz joe epa gov BCFwin and Biowin Bob Boethling Exposure Assessment Branch 7406 US Environmental Protection Agency 401 M St SW Washington DC 20460 boethling bob epa gov 36 D Green Solvents Reaction Conditions 1 Description of the Module The Green Solvents Reaction Conditions module provides information on green reaction conditions as well as databases of examples and physic
42. n Synthetic Reactions module of the GCES and Eliminate the use of the solvent toluene If a solvent is necessary find a less toxic replacement This reduces both the concern for Tier 2 chemicals and the total amount of chemicals subject to EPA regulation A less hazardous substitute solvent may be found by comparing the physicochemical properties of toluene with potential alternatives in the Green Solvents Reaction Conditions Database module of the GCES or in other literature sources Sometimes there may not be a green alternative or the available alternative is not feasible In these cases it may be possible to recover excess chemicals In this example some recovery suggestions are Recover more of the product This would reduce the amount of Tier 2 waste and Recover more of the toluene if an alternative solvent is not available This would reduce the amount of Tier 2 waste and ultimately the net amount of EPA regulated chemicals used in the process Finally some unrecoverable feedstocks may be used in a large excess If there is no suitable alternative feedstock available then it may be possible to limit the excess amount to the absolute minimum necessary for an acceptable yield For example if ethanamine cannot be replaced then you may be able to limit the excess used Ethanamine waste amounts to 2746 of the production volume in this sample synthesis In practice such a large excess of ethanamine is used to consume HCI generated in
43. nding buttons Nitriles are substances that contain the cyano CN group Nitriles represent a large commercial category of chemical substances that include among others drug products solvents and synthetic intermediates While a variety oftoxic effects have been reported for specific nitriles the two major toxic concerns for this chemical class are acute lethality and osteolaythrism A comprehensive discussion of nitrile toxicity and how safer nitriles can be designed is available DeVito Stephen C Designing Safer Nitriles IN Designing Safer Chemicals Green Chemistry for Pollution Prevention DeVito 3 0 and Garrett R L Editors ACS Symposium Series No 640 American Chemical Society Washington DC 1996 pages 194 223 oxic mechanisms and structure activi i ips of nitrile toxicity Qualitative toxicity assessment of a planned nitrile Guidance for designing safer nitriles Figure 33 Nitriles Screen The Toxic mechanisms and structure activity relationships of nitrile toxicity button 33 brings up a topic page that displays information on the toxicity and structure activity relationships for toxic responses This page has further links to other screens containing additional toxicity information The Qualitative toxicity assessment of a planned nitrile button brings up a series of questions designed to determine the acute lethality or osteolathyrism of a particular nitrile based on structure activity relationships The descr
44. nterest or you can return to the SMART Menu Screen Figure 7 by clicking on File Close W Microsoft Access BEE File MAA Help What is the SMART Program for Pollution Prevention z What is the EPA s New Chemicals Program ox v How Does the SMART Relate to Pollution Prevention What is the Goal of the SMART Program he How Does EPA Meet This Goal prevention ethic and provides an OPE How Does the EPA Select PMN Submissions for SMART Review RE A SY Won un Can eae SCA BMT Pro i Ps i als Program of TSCA How are Chemicals Classified for SMART Review he How are Chemicals Identified and Targeted PA states that Tk Howis the Quantity of Each Chemical Substance Determined es that pollution should be pre How Does the Agency Decide Whether to Perform a Detailed Review be prevented should be recycled in ant How Does EPA Perform Detailed Pollution Prevention Assessments prevented or recycled should be U How Does EPA Notify PMN Submitters of the Results E na HIE How Can get More Information d Source reduction is defined in part as any practice which reduces the amount of any hazardous substance pollutant or contaminant entering any vaste stream or otherwise released into the environment including fugitive emissions prior to recycling eatment or disposal and reduces the hazards to public health and the environment associated with the release of such substances pollutants or contaminants hereas the New Ch
45. ocesses to replace a more hazardous materials with a less hazardous ones Designing Safer Chemicals an information module detailing the design of safer chemicals especially useful in this module is check list to determine eligibility for the Agency s polymer exemption from reporting requirements under the Toxic Substances Control Act TSCA Green Solvents Reaction Conditions Database an information module detailing green solvents and reaction conditions a database containing a list of solvents with selected physiccal chemical data for use in identifying solvent substitutes Green Chemistry Reference Sources a searchable database containing literature references for the four modules as well as other Green Chemistry references Taken together the modules of the GCES provide a source of information on Green Chemistry that may be used as an effective pollution prevention tool The GCES was initially developed by Syracuse Research Corporation SRC under contract with the Office of Pollution Prevention and Toxics OPPT of the U S Environmental Protection Agency EPA The current version being distributed is version 0 99 The SMART module is fully operational The other modules are operational and are still being developed EPA would appreciate feedback on both the content and ease of use of the system Please address your comments to Dr Carol A Farris or Dr Gregory L Fritz Green Chemistry Expert System Industrial Chemistry
46. ochemical properties for over 600 solvents of varying hazard many of which are commonly used Learn more about the state of the science by browsing the Green Solvents Reaction Conditions Find replacement solvents by searching for solvents that approximate the set of properties of the solvent you would like to replace The GCES does not contain toxicity data for these solvents but does contain regulatory list information in addition to global warming potential and ozone depletion potential Using this information you may qualitatively evaluate health and environmental hazards For a more quantitative hazard evaluation you should determine the toxicity of solvents by other means after identifying alternatives through this module In the current version of the GCES this module contains a limited number of examples more will be added in future versions Green Solvents Reaction Conditions Module This module provides information on greener solvent systems Learn more about green solvent systems search for a replacement solvent based on physiochemical properties browse the solvent database or search a database of examples Green Solvents Reaction Conditions Search Solvents by Physiochemical Properties Browse Solvents Database Search Examples Return to Main Menu Figure 36 Green Solvents Reaction Conditions Main Screen 2 Using the Module When you select the Green Solvents Reaction Conditions module from the main menu you wil
47. ou have completed your search you can choose to Perform Another Search or exit the Green Synthetic Reactions module by clicking on the Close Module button or by selecting File Close Module from the menu at the top of the screen If no records were found to match your search criteria your criteria may have been too specific In this case you may want to click on Perform Another Search and broaden the search terms used However the limited size of the database in this version of the GCES may mean that this module simply does not contain the reference you are looking for For example at present there is no information on chromium replacements in this module The amount of information that the GCES can index is limited and a library search may be necessary However you may check www epa gov greenchemistry to see if an update to the GCES is available 31 C Designing Safer Chemicals 1 Description of the Module The Designing Safer Chemicals module provides you with qualitative information regarding the toxicities of compounds within certain chemical classes or that have certain uses Based on structure activity relationships this module will help you to estimate the qualitative toxicity of a particular chemical in the classes covered to understand their mechanism of toxicity and to predict which structural modifications that may reduce how hazardous a compound is Information is organized by class or use or in the case of environmental toxicity
48. ough it is the best alternative The SMART module of the GCES allows you to analyze the amount of chemical waste produced by a manufacturing process In addition the module classifies the chemicals according to their hazard using EPA criteria and displays general concerns for these chemicals allowing you to target specific chemicals for reduction or elimination from the synthesis By identifying green alternatives to your initial process and entering them into the SMART module e g changing the amount of material recovered or using less hazardous feedstocks and reagents you can repeat the analysis to observe changes and reduce or eliminate the use and creation of hazardous materials The Agency realizes that changes in chemical syntheses made for source reduction must be both chemically and economically feasible The SMART module may lead to the development of a green synthesis but the user must ultimately determine the economic reasonableness of any new synthesis including such things as the cost of feedstocks and other reagents yield equipment modifications energy use etc The SMART module contains mathematical algorithms that perform a series of calculations for a given reaction process This module performs mass balance calculations based on user entered data and classifies the hazardous nature of each material used or formed in the process using established EPA guidelines You will be asked for some general information regarding your
49. ould like to continue Figure 16 Clicking on No will return you to the chemical ID screen Figure 14 You might want to do this if you realize that you entered a CAS RN incorrectly and want to edit it After correcting the CAS RN on the chemical ID screen select Find to continue ID not found E ID Number 001111 11 1 was not found in the 3 lookup table Would you like to continue Figure 16 CAS Registry Number Not Found Screen If you select Yes you will have to enter the information on molecular weight chemical name and SMILES notation to the blank Chemical Information Screen Figure 17 Click on Add above information to lookup table to save this chemical and its associated information for 16 automatic retrieval in the future You do not need to add information to the Lookup Table if the chemical will only be used for one reaction Caution should you need to leave the GCES to find some of the information for this form you should save your work by adding the information to the lookup table before exiting ID 001111 11 1 MW SMILES Name Add above information to lookup table Qty kgs Qty Recovered kgs Role Feedstock 2 Equivalents Figure 17 Chemical Information Screen for Data entry If you do not have a CAS RN you may click on the Other Unique Identifier box and enter a chemical identity of your choice numbers letters or both in the chemical ID box Chemical name ab
50. pen Saved Reaction The reaction ID box will appear clicking on the down arrow will produce a list of saved reaction identities for you to choose from Then click on the reaction ID of your choice Figure 10 Figure 10 Open Saved Reaction Screen Two sample reactions are provided with this GCES distribution The examples in this manual use the data in Sample 1 The chemical reaction and associated data for Sample 1 are shown in Figure 11 The associated reaction information screen is shown in Figure 12 12 CAS Registry Number 75 04 7 Ethanamine ethyl amine 75 44 5 Carbonic dichloride phosgene g NO y 647 01 0 Hydrochloric acid F Feedstock S Solvent C Coproduct P Product Equivalents Reaction proceeds with 87 7 yield Produce 2 batches per year 108 88 3 Methylbenzene toluene 7647 01 0 Hydrochloric acid 04 bisphenol A s Epiri 5 ENS Chemical Name Role Eq Amount Amount CAS Name trivial name Charged or Recovered Formed per per Batch Batch kgs 10 000 8 000 7 409 6 500 2 On HO OH 4 HCI O O ANDA Figure 11 Sample 1 Chemical Reaction and Associated Data After editing click k continue to return to the Reaction ID Sample 1 chemical specific information Batches year 2 Reaction Yield 96 87 7 Figure 12 Reaction Information Screen Sample 1 Please note that once you enter a reaction ID you may save the reaction at any
51. pleted the SMART review of your process look for information in the modules suggested below See the Green Synthesis module You may be able to find an altemative to this synthetic method See the Green Solvents Reaction Conditions module You may be able to find an altemative to the solvent used in this process See the Designing Safer Chemicals module You may be able to find information on how to reduce the toxicty of the product Figure 25 Green Suggestions Screen gt To Estimate the Hazard of the Chemical Process An estimate of the hazardous nature of the chemical process can be viewed by clicking on Level of Concern on the SMART Assessment Screen Figure 20 A screen will be displayed showing a standard list of opportunities for pollution prevention P2 listed in order of descending level of concern Figure 24 A ball marker is displayed to the left of each concern if it applies to Level of Concern The goal of Pollution Prevention is to reduce or eliminate the use and generation of hazardous substances If any of the levels of concern are bulleted efforts should be made to reduce or eliminate the substances s leading to this concern Tier 1 chemicals are either used or produced Chemicals on the EPCRA CAA 112 2 or HAPS lists are present Significant quantities of tier 2 chemicals are present as waste Significant quantities of tier 1 tier 2 tier 3 chemicals are present as waste Significant quantities of tie
52. r 3 chemicals are present as waste Excessive total waste is present Figure 24 Level of Concern Screen 23 the particular chemical process used for this SMART Assessment Although it is true that the concerns are ranked it should always be noted that if any concern exists there may be an opportunity for source reduction or other pollution prevention A process that triggers only the concerns at the bottom of the list should not be regarded as benign just because none of the higher concerns are present In the Sample 1 reaction Figure 10 the concerns are A Tier 1 chemical phosgene is used EPA regulated chemicals phosgene toluene bisphenol A ethyl amine are used High levels of Tier 2 waste toluene bisphenol A ethyl amine HCl product are present High levels of Tier 1 Tier 2 Tier 3 phosgene toluene bisphenol A ethyl amine HCl product waste are present and The total waste is excessive Now that you have identified the sources of concern you can begin to develop strategies for eliminating or reducing them EPA strongly encourages replacement of hazardous chemicals with less toxic alternatives wherever possible In this sample case possible suggestions might be Replace phosgene with dimethyl carbonate which has been used commercially as a substitute for phosgene This removes the concern for Tier 1 chemicals and reduces the use of a regulated chemical References to this process can be found in the Gree
53. re stored on your hard drive or a removable You can check the location of these files using File Manager or Explorer The other three paths are for links to estimation software bcfwin bioconcentration factor biowin biodegradation and ecowin ECOSAR aquatic toxicity These are not necessary to run the GCES the links are provided for users who have these estimation programs For more information see the Designing Safer Chemicals module in section VI C V RUNNING HELP IN THE GCES You can access the help program that supports GCES at any point in the program by clicking on Help on the menu bar at the top of the screen or by pressing the Fl key The GCES uses context sensitive help the help topic is related to the module you are working in For example if you are in the Green Solvents Reaction Conditions module clicking on Help will display information on that particular module You may however see the contents of all of the topics in the help program by clicking on Contents in the Help Screen see Figure 6 From this help screen you may access any of the topics To print a help topic select File Print from the menu bar at the top of the help screen or select Print from the lower menu bar To exit help either select File Exit on the help screen menu bar or with Windows 95 click on the x in the top right corner of the help screen and you will return to the point in the GCES program where you accessed help amp Green Che
54. s topic Weininger D J Chem Inf Comp Sci 1988 28 1 31 if you are unfamiliar with this notation An expanded discussion on SMILES notation is also available on the World Wide Web at http esc syrres com ESC docsmile htm Some chemistry drawing packages such as ChemDraw ConSystant Kekule will generate a SMILES notation from a chemical structure 9 For certain chemical structures primarily salts and inorganics the standard SMILES notations have been modified in the SMART module to be compatible with other Syracuse Research Corporation products Entering a standard SMILES notation for one of these classes of molecules will result in an error message even though the SMILES notation is correct When prompted if you want to edit the notation click on No and proceed as prompted The SMART analysis may not be able to recognize the functional groups in that molecule so it may not be able to classify the hazard tier correctly However the calculations will proceed normally After the SMART data entry is complete the program will analyze all the wastes produced in the reaction and provide you with the total amount of waste produced in kg year and as a percentage of the total annual production volume separated into four hazard categories which we call Tiers 1 through 4 To assist you in interpreting the results the program will provide a qualitative indication of the level of concern that is triggered by the reaction process If chemical
55. s Screen Figure 2 At this point you must decide if you are going to load the large data tables approximately 20 Mbytes on to your computer You may choose to save the large data tables to your hard drive or a removable drive If you choose to load the data tables to your hard drive select Copy the supplemental databases to the GCES directory If you choose to load the data tables to another location select Copy the databases to and enter a path drive and directory where you want the tables saved Click Continue to complete the installation If you cancel this phase of the installation rerun the entire installation to ensure that all components get installed correctly Green Chemistry Expert System Installation Options The GCES contains two large supplemental databases that use approximately 20 megabytes 20 MB of disk space These databases can be loaded onto the same directory as the GCES main program or to another location C Copy the supplemental databases to another directory Path Copy the supplemental databases to the GCES directory Directory path the installation was started from CAGCESINST Continue Cancel Installation Figure 2 Installation Options Screen If after the initial installation you may want to change to the other installation option you can do so manually You can move the database files lookup mdb and greenref mdb to another location using File Manager or Windows Explorer j
56. s in Tiers 1 or 2 are present the program will direct you to the other modules as appropriate Please note that the algorithms developed for this module have been designed for and tested with single step reactions that produce a single discrete chemical product The program is not appropriate for polymers or reactions with multiple products The individual reactions of a synthetic sequence may be run sequentially Simply enter the recovered mass of product for each step as the amount of feedstock charged in the subsequent reaction 2 Starting the SMART Module When you choose the SMART module from the main system menu the SMART module menu will appear Figure 7 Welcome to the GCES SMART Module This system is designed to provide users with information and tools to make new or existing manufacturing processes less hazardous to human health and the environment Use of the system does not exempt the user from any regulatory responsibilities It should not be used for reporting or regulatory activities i understand proceed to SMART Assessment About the SMART Assessment Return to Main Menu Figure 7 SMART Menu Screen 10 To learn more about the SMART module click on About the SMART Assessment You will then see the first information screen What is the SMART Program for Pollution Prevention Figure 8 From there you can continue looking at other topics by clicking on SMART on the top menu bar and selecting a topic of i
57. time by selecting File Save or File Save As from the menu at the top of the screen Clicking on Continue when you are finished with the reaction information screen brings up the summary screen showing your chemical specific data Figure 13 At this point you need to enter all of the chemical substances used or formed during the manufacturing process if they have not been entered and saved previously GCES SMART Module Id Sample 1 Yield 100 Batches 2 Volume kg 13000 Hydrochloric acid p00075 04 7 Feedstock JEthanamine m 000075 44 5 Feedstock Carbonic dichloride ES 000030 05 7 Feedstock Phenol 4 4 1 methylethylidenejbis m Product Product Product 000103 83 3 Solvent Benzene methyl KIKI G Emy nau Cn peto Ea Reaction Dato smart Review Figure 13 Chemical Summary Screen 14 gt To Add a Substance to a Reaction Begin by selecting Entry Add from the Chemical Summary Screen Figure 13 and providing information on the chemical you wish to add You will be prompted to enter a chemical identifier Figure 14 either a CAS Registry Number or another unique identifier if you do not have a CAS RN It is to your advantage to find and use a CAS Registry Number for each chemical in the reaction if one exists Enter Chemical ID CAS Registry Number Other Unique Identifier Figure 14 Chemical Identification Screen You may enter CAS RNs with or without leading zeros but they m
58. ugh the preceding error message appears Adjust the amounts charged or recovered to correct the error Another possible error may occur if the calculated yield of the reaction exceeds 100 This may occur if the amount of product formed in the reaction is too high if the amount of feedstock or reagent charged is too low if the amount of feedstock recovered is too high or if there is a rounding error You can simulate this error using the Sample 1 reaction data and changing the Quantity Produced and Quantity Recovered for the product Figure 15 to 8 000 Kg and running the SMART assessment Figure 27 illustrates this error Data Entry Error A data entry error was found The calculated yield for this reaction is 107 9721 Possible causes include x The amount of product formed is too high The feedstock or reagent amount is too low The amount of feedstock recovered is too high or rounding error has occured Please check the reaction and try again Figure 27 Error Message Yield gt 100 If you see this error message during a SMART assessment you should check each of the possible causes listed on the screen Clicking on OK will take you back to the Chemical Summary Screen Figure 13 from which you may correct the error The Chemical Information Screen Figure 15 allows you to change the CAS RN identifying number molecular weight SMILES notation and chemical name If you change the ID number for example from 108
59. ust be sure to keep them both in the same directory After you have moved these files be sure to change the path for external tables in the GCES preferences see Figure 5 to the new directory containing the database files IV STARTING THE GCES For purposes in this manual it should be noted that the terms select choose and click are used interchangeably and simply mean for you to press the left button on your mouse to select the item of choice To facilitate the understanding of the GCES program options menu items and push buttons are highlighted in bold in this manual Please note that the graphics appearing in this manual were developed using Windows95 and some screens may appear slightly different to Windows 3 x users To access the GCES program in Windows 3 x double click on the icon that the install program created in the GCES program group Windows95 users can select Start Programs Green Chemistry Expert System GCES The program will load and you will see the GCES startup screen Figure 3 Green Chemistry Expert System Industrial Chemistry Branch Office of Pollution Prevention and Toxics U S Environmental Protection Agency Developed under contract by Syracuse Research Corporation Version 0 99 Figure 3 GCES Startup Screen Note the menu bar at the top of the screen This menu bar contains information on the items available to choose from at each point in the program For example when the startup w
60. ust have dashes Click on Find to search for the chemical in the SMART Lookup Table a database of over 60 000 chemicals containing information on CAS RN chemical name molecular weight and SMILES notation If the CAS RN you entered is in the Lookup Table then the chemical name molecular weight and SMILES notation will be provided on the Chemical Information Screen Figure 15 For example assume that you want to add ethanamine After you enter the CAS Registry number 75 04 7 and select Find the Chemical Information Screen will be displayed Figure 15 Note you cannot enter a chemical twice for the same reaction If for some reason the Lookup Table lookup mdb is not found the Preferences Screen Figure 5 will pop up Check the path for the external databases and try the data entry again CAS Registry Number 000075 04 7 SMILES NCC Name Eisen Qty kgs Qty Recovered o Role Feedstock 2 Equivalents Lm em Figure 15 Chemical Information Screen 15 Once the chemical information is displayed fill in the quantity used or produced in the process kg batch equivalents from the stiochiometry of the reaction amount recovered kg batch and the role the chemical plays in the process select from the drop down list For the purposes of the SMART analysis a reaction can only have one product Other compounds that are formed during the reaction are identified either as coproducts or byproducts Coproduct any ch
61. will perform a chemical name search Similarly you can conduct a CAS RN search by clicking in the CAS RN field before you select Search Search Database The search command brings up the Microsoft Access Search Screen Figure 40 You may find it helpful to move the Search Screen so that it does not obscure you view of the list of solvents Find in field Chemical Name Find What chloro ss S Where Any Part of Field y Direction Search In O Up Current Field All Fields Down Match Case Search Fields as Formatted Figure 40 Microsoft Access Search Screen Find What Type the alphanumeric search string you want to find either a CAS RN or a chemical name You may type either the full search term or only a small part i e a sub string based on the choice of the Where setting Where This can be used to perform a full name or sub string search Click the drop down arrow to display a list of search locations Any Part of Field e g the results of searching for chloro will include both dichlorodifluoromethane and methane tetrachloro Match Whole Field will provide an exact match and Start of Field will search for the text string at the beginning of a field Search In The default setting is Current Field Either setting is acceptable Direction This provides the direction of the search and is typically left in the default setting Down which searches from the top o

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