Handbook of Pollution Prevention and Cleaner Production Vol. 3: Best Practices in the Agrochemical Industry

319 Pages·2010·2.78 MB·English

by  Nicholas P Cheremisinoff Consulting Engineer

Handbook of Pollution Prevention and
Cleaner Production
Volume 3
This page intentionally left blank
Handbook of
Pollution Prevention and
Cleaner Production
Volume 3
Best Practices in the
Agrochemical Industry
Edited by
Nicholas P Cheremisinoff and Paul E. Rosenfeld
AMSTERDAM BOSTON HEIDELBERG LONDON
(cid:1) (cid:1) (cid:1)
NEWYORK OXFORD PARIS SANDIEGO
(cid:1) (cid:1) (cid:1)
SANFRANCISCO SINGAPORE SYDNEY TOKYO
(cid:1) (cid:1) (cid:1)
WilliamAndrewisanimprintofElsevier
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Contents
1 IndustryandProducts 1
1.1 Introduction 1
1.2 Fertilizers 2
1.3 PesticidesandOtherAgriculturalChemicals 4
1.4 FederalInsecticide,Fungicide,andRodenticideAct(FIFRA) 10
1.5 ManufacturingTechnologies 10
2 PollutionandPollutionPrevention 25
2.1 SourcesofPollution 25
2.2 CaseStudy 25
2.3 EnvironmentalAspects 53
2.4 RecommendedPollutionPreventionandControlOptions 56
2.5 SourceReductionOpportunities 59
2.6 WaterManagementandTechnicalChallenges 60
2.7 SteamLossesandSensibleHeatRecovery 62
2.8 PollutionPreventionOpportunities 68
3 ToxicandDangerousProperties 81
4 Atrazine 215
4.1 Introduction 215
4.2 Regulations 215
4.3 HowAtrazineWorks 216
4.4 BreakdownProducts 218
4.5 WaterContaminationIssues 219
4.6 SyngentaAtrazine MonitoringProgram(AMP) 220
4.7 HealthEffects 225
4.8 AtrazineExposureCaseStudies 226
4.9 AtrazineRemovalTechnologies 228
4.10 AlternativestoAtrazine 229
5 1,2,3-Trichloropropane(TCP) 233
5.1 Introduction 233
5.2 ToxicologyandHealthRisks 234
5.3 RegulationsandStandards 236
5.4 TheTCP(cid:1)DCPFumigantLink 237
5.5 GroundwaterContaminationCaseStudies 239
5.6 AnotherToxicSoilFumigant:Dibromochloropropane 239
5.7 TreatmentandRemediationTechnologies 242
vi Contents
6 DDTandRelatedCompounds 247
6.1 Introduction 247
6.2 HistoryofDDT:ProductionandUses 247
6.3 Distribution,Transport,andEnvironmentalFate 250
6.4 ImpactonWildlife 252
6.5 HealthEffects 253
6.6 CurrentUse,MalariaControversy,andAlternatives 255
7 AgentOrange 261
7.1 Introduction 261
7.2 ChemicalComposition 261
7.3 UsesintheVietnamWar 262
7.4 HealthEffects 264
7.5 Government Response 265
7.6 Litigation 266
7.7 OtherUses 267
8 PesticideResidueinFoods 269
8.1 FederalMonitoringandSurveillanceofResidueContamination 269
8.2 ModificationofPesticides DuringPost-Harvest 272
8.3 TheFoodQualityProtectionAct(USEPA,2008) 272
8.4 OrganicFoods 273
8.5 The‘DirtyDozen’ 274
8.6 MeasuringResidualLevels(Nasreddineetal.,2002) 275
8.7 AcuteExposuresandContaminationVariability 276
9 EPAScreeningLevelsandPesticideStatus 281
Index 307
1
Industry and Products
1.1 Introduction
The fertilizer, pesticide, and agricultural chemical industry sector is diverse. The
justification for this industry is that as the world population increases, crop lands
are increasingly strained and unable to meet the growing demand for food without
employing some method of crop enhancement. There are generally believed to be
fivecommonpracticescapableofmeetingthegrowingdemand:
(cid:1) increasingtilledacreage
(cid:1) improvingplantstrains
(cid:1) introducingorexpandingirrigation
(cid:1) controllingpestsbychemicalorbiologicalmethods,and
(cid:1) initiatingorincreasingfertilizerusage.
Thelasttwomethodshavecreatedalargeagrichemicalindustrywhichproduces
a wide variety of products designed to increase crop production and protect crops
from disease and pests. Along with the benefits there have been increasingly nega-
tiveimpactsontheenvironment,variousnaturalresources,andtohumanhealth.
Plantliferequires18elementstogrow,withthemostimportantonesbeingoxy-
gen, carbon, hydrogen, nitrogen, phosphorous, and potassium. Oxygen, carbon, and
hydrogen are obtained from the atmosphere and water, while nitrogen, phospho-
rous,andpotassiumarenaturallyobtainedfromsoils.Undercurrenthigh-yieldpro-
duction methods, soils are stripped of the essential nutrients, thereby requiring the
addition of fertilizers, particularly those comprised of nitrogen, phosphorous, and
potassium in order to resupply the land. The additional 12 essential nutrients are
generally maintained in soil at sufficient levels for plant growth, but they may be
addedtosomefertilizerformulationstoimprovecropyields.
There are more than 8000 establishments identified by the United States EPA
that manufacture, formulate, and package pesticides and other agricultural chemi-
cals. Many of these are relatively small establishments and are comprised of facili-
ties that have a primary line of business other than producing pesticides and other
miscellaneous agricultural chemicals. The industry is therefore diverse with a sig-
nificantnumberofstakeholders.
Thischapterprovidesanoverviewoftheindustryandvariouschemicalproducts
and building blocks used in the manufacture of agrochemicals. From this general
overview, we will build on an understanding of the pollution issues stemming from
HandbookofPollutionPreventionandCleanerProduction.DOI:10.1016/B978-1-4377-7825-0.00001-7
©2011ElsevierInc.Allrightsreserved.
2 HandbookofPollutionPreventionandCleanerProduction
the industry and then discuss pollution prevention and responsible care practices in
subsequentchapters.
1.2 Fertilizers
Therearetwoimportantclasses:nitrogenousandphosphaticfertilizers.
1.2.1 Nitrogenous Fertilizers
The nitrogenous fertilizer industry includes the production of synthetic ammonia,
nitric acid, ammonium nitrate, and urea. Synthetic ammonia and nitric acid are
used primarily as intermediates in the production of ammonium nitrate and urea
fertilizers. The following is a list of primary specific products classified as nitroge-
nousfertilizers:
(cid:1) ammonialiquor
(cid:1) ammoniumnitrate
(cid:1) ammoniumsulfate
(cid:1) anhydrousammonia
(cid:1) aquaammonia
(cid:1) fertilizers,mixed,producedinnitrogenousfertilizerplants
(cid:1) fertilizers,natural
(cid:1) nitricacid
(cid:1) nitrogenfertilizersolutions
(cid:1) plantfoods,mixedinnitrogenousfertilizerplants
(cid:1) urea.
Synthetic ammonia is ammonia that has been synthesized from natural gas in
which natural gas molecules are reduced to carbon and hydrogen. The hydrogen is
then purified and reacted with nitrogen to produce ammonia. About 75% or more
of the synthetic ammonia produced in the United States is used as fertilizer, either
directly as ammonia or indirectly after fertilizer synthesis into urea, ammonium
nitrate, and monoammonium or diammonium phosphates. Roughly one-third of the
fertilizer nitrogen is applied directly to the land as anhydrous ammonia. The
remaining25%ofammoniaproduced isused asrawmaterialinthemanufacture of
polymericresins,explosives,nitricacid,andotherproducts.
Nitric acid is formed by concentration, absorption, and oxidation of anhydrous
ammonia.About70%ofthenitricacidproducedisconsumed asanintermediatein
the manufacture of ammonium nitrate (NH NO ), which is largely used in fertili-
4 3
zers. Up to 10% of the nitric acid produced is used in adipic acid manufacturing
which is an intermediate in nylon production. Explosive manufacturing uses nitric
acid for organic nitrations to produce nitrobenzene, dinitrotoluenes, and other
chemical intermediates. Otherenduses of nitric acidare goldandsilver separation,
military munitions, steel and brass pickling, photoengraving, and acidulation of
phosphaterock.
IndustryandProducts 3
Ammonium nitrate is produced by neutralizing nitric acid with ammonia. Up to
20% of ammonium nitrate is used for explosives and the remainder for fertilizer
production. Liquid ammonium nitrate may be sold as a fertilizer, generally in com-
bination with urea. Liquid ammonium nitrate may also be concentrated to form an
ammonium nitrate ‘melt’ for use in solids formation processes. Solid ammonium
nitrate may be produced in the form of prills, grains, granules, or crystals. Prills,
round or needle-shaped aggregates, can be produced in either high- or low-density
form,dependingontheconcentration ofthemelt.High-densityprills,granules,and
crystals are used as fertilizer, grains are used solely in explosives, and low-density
prillscanbeusedaseitherfertilizerorexplosives.
Urea (also known as carbamide or carbonyl diamide) is produced by reacting
ammonia with carbon dioxide. Roughly 85% of urea solution produced is used in
fertilizer mixtures, with 3% used as animal feed supplements and 12% used for
plastics and other uses. Urea is marketed as a solution or in solid form. Most solids
are produced as prills or granules for use as fertilizer or protein supplement in ani-
malfeed,andinplasticsmanufacturing.
Ammonium sulfate is not economically feasible to produce for use as a fertil-
izer. However, it is formed as a by-product of other process such as acid scrubbing
ofcoke ovengas, syntheticfiberproduction,andtheammoniationofprocess sulfu-
ricacid.
1.2.2 Phosphatic Fertilizers
The phosphatic fertilizer industry is organized into three major segments: phospho-
ricacid,granularammoniumphosphate,andnormalandtriplesuperphosphate.The
followingisalistofimportantproducts:
(cid:1) ammoniumphosphates
(cid:1) calciummeta-phosphates
(cid:1) defluorinatedphosphates
(cid:1) diammoniumphosphates
(cid:1) fertilizers,mixed,producedinphosphaticfertilizerplants
(cid:1) phosphoricacid
(cid:1) plantfoods,mixedinphosphaticfertilizerplants
(cid:1) superphosphates,ammoniatedandnotammoniated.
Phosphoric acid (H PO ) can be manufactured using either a wet or a thermal
3 4
process to react phosphate rock with sulfuric acid. Approximately 96% of the
domestic phosphoric acid produced is made using the wet process. Wet process
phosphoric acid has a phosphorous concentration typically ranging from 26(cid:1)30%
asphosphorouspentoxide(P O )andisused intheproductionofammoniumphos-
2 5
phates and triple superphosphates. Thermal process phosphoric acid is used in the
manufactureofhigh-gradechemicalswhichrequirehighpurity.
Ammonium phosphate (NH H PO ) is produced by reacting phosphoric acid
4 2 4
with anhydrous ammonia. Both solid and liquid ammonium phosphatic fertilizers
are produced. The most common ammonium phosphatic fertilizer grades are