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  • 8/18/2019 Better ETP Performance in View of Zinc Technology

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    Birla In!tit"te of Technology an$ Science; Pilani

    ACKNOWLEDGEMENT

    I wo"l$ li/e to e=pre!! my !incere than/! to Birla In!tit"te of Technology an$

    Science for giving me thi! won$erf"l opport"nity to "n$ergo a training program at

    thi! pre!tigio"! organi>ation8

    I wo"l$ li/e to e=pre!! my gratit"$e to :r8 Si$$arth Bener?ee; the 7nit 4ea$ an$

    &ra!im In$"!trie! for allowing me to $o thi! pro?ect8

    I am than/f"l to .r8 0apil 9hat"rve$i for g"i$ing me thro"gho"t the pro?ect an$

     provi$ing me all the nece!!ary $ata an$ al!o coor$inating with other $epartment!

    for me8

    I am al!o than/ to :r8 Samir 0ale; my in!tr"ctor for hi! g"i$ance $"ring thi!

     practice !chool II program witho"t which it wo"l$ not have #een a !"cce!! an$ a!

    goo$ a learning e=perience a! thi!8

      .eepa/ 0a!hyap

      :8E8 9hemical Engineering

      .epartment of 9hemical Engineering

      Birla In!tit"te of Technology an$ Science; Pilani

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    CERTIFICATE

    Thi! i! to certify that .eepa/ 0a!hyap  have !"cce!!f"lly complete$ the Practice

    School II pro?ect on the topic @Better ETP performance in view of Zinc

    Technology "n$er o"r &"i$ance a! a part of the partial f"lfillment of the co"r!e8

    Dr. Kapil Chaturvedi  :anager; Effl"ent Treatment Plant *ETP+

      &ra!im In$"!trie!

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    BIRLA INSTITTE OF TEC!NOLOG" AND SCIENCE

    #ILANI $RA%AS!TAN&

    #RACTICE SC!OOL DI'ISION

    Stati() &ra!im In$"!trie!

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    BIRLA INSTITTE OF TEC!NOLOG" AND SCIENCE

    #ILANI $RA%AS!TAN&

    #RACTICE SC!OOL DI'ISION RESPONSE OPTION SHEET 

    Stati()- &ra!im In$"!trie! ation8

    Si0)ature (* Stude)t Si0)ature (* #S Fa/ult2

    .eepa/ 0a!hyap :r8 Samir R 0ale

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    :8E8 9hemical Engg8 BITS PS-II ac"lty

    9ontent!

    SR8 NO8 PARTI97ation Tan/

    581 Ne"trali>ation Tan/

    58( Primary 9larifier

    585 Aeration Tan/

    J

    J

    J

    )

    )

    )

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    586 Secon$ary 9larifier

    58' Sl"$ge Thic/ener

    58 Belt Pre!!

    58J Ka!tewater .i!po!al

    32

    32

    32

    68 Propo!e$ Zn technology 33

    '8 Role of >inc in !pinning proce!! 3(

    8 inc "!ing thiopho!phinic e=tractant

    12

    38 proce$"re for the $etermination of aci$; >inc; an$

    magne!i"m in wa!te water 

    11

    3J8 9oncl"!ion 15

    3)8 Reference 15

    3. Gra+im i)du+trie+ Ltd.

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    &ra!im i! a flag!hip company of the A$itya Birla &ro"p an$ i! to$ay a $ominant

     player in the man"fact"ring of Gi!co!e Staple i#er *GS+; an e=tremely ver!atile

    te=tile fi#re that ha! characteri!tic! !imilar to cotton8 The "nit wa! e!ta#li!he$ in

    3)65 with pro$"ction capacity of 36 TP. with Plant E%"ipment importe$ from

    .o#!on Barlow of 7808

    The plant ha! grown organically with c"rrent in!talle$ capacity of 536 TP.8 Kith

    "!e of entirely in$igeno"! re!o"rce! incl"$ing raw material!; /now-how an$

    e%"ipment &ra!im ha! emerge$ a! one of the worl$L! mo!t co!t-efficient GS

     pro$"cer!8

    The man"fact"ring facility i! locate$ clo!e to river 9ham#al at Nag$a *:P+; a

    !mall town e=actly mi$ ,way on the rail ro"te from New .elhi to :"m#ai8

    The company ha! al!o e!ta#li!he$ an engineering $ivi!ion to man"fact"re the plant

    an$ machinery "!e$ for pro$"cing GS an$ i! a ma?or e=porter to !o"th ea!t an$

    far ea!tern co"ntrie!8

    The 9ompany i! committe$ to innovation an$ creativity an$ ha! !ignificant

    !trength! in Re!earch .evelopment8 In colla#oration with the Birla Re!earch

    In!tit"te for Applie$ Science! at Nag$a; the 9ompanyL! R. team! en$eavo"r to

    ma/e technology wor/8 Thi! i! very important !ince GS man"fact"ring proce!! i!

    highly energy inten!ive an$ it! contri#"tion to total co!t of pro$"ction i! appro=83186M8 The company ha! it! own thermal plant for electricity nee$!8 

    &ra!im to$ay i! a $ominant player in the 'i+/(+e Staple Fi,er $'SF+ !egment an$

    thi! i! partic"larly commen$a#le #eca"!e of it! "!e of entirely in$igeno"! re!o"rce!

    incl"$ing raw material!; /now-how an$ e%"ipment8 An innovative an$ re!earch-

    oriente$ organi>ation; &ra!im ha! emerge$ a! one of the worl$L! mo!t co!t-

    efficient GS pro$"cer! $"e to it! integrate$ operation!8

    &ra!im i! al!o In$iaL! large!t pro$"cer of So$i"m S"lphate , a #ye-pro$"ct of GS

    man"fact"re8 Thi! chemical i! "!e$ wi$ely in paper p"lp; $etergent; gla!! an$

    te=tile! in$"!trie!8

    P"lp i#er B"!ine!! contri#"te! !ignificantly to the National E=che%"er #y way

    of E=ci!e $"ty an$ al!o to In$iaL! foreign e=change re!erve! thro"gh e=port of P"re

    an$ Blen$e$ arn a! well a! fa#ric! an$ :a$e-"p! #a!e$ on GS8

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    ig83 :an"fact"ring Proce!! of GS

    4. Ba+i/ #ri)/iple+ (* Ra2() Fi,er #r(du/ti() 

    Rayon i! man"fact"re$ #y three $ifferent chemical proce!!e!; namely the vi!co!e

     proce!!; the cell"lo!e acetate proce!!; an$ the c"prammoni"m proce!!8 In In$ia

    mo!t of the "nit! pro$"ce vi!co!e rayon8 In the pro$"ction of rayon; p"rifie$ cell"lo!e i! chemically converte$ into a !ol"#le compo"n$8 A !ol"tion of 

    thi! compo"n$ i! pa!!e$ thro"gh the !pinneret to form !oft filament! that are then

    converte$ or @regenerate$ into almo!t p"re cell"lo!e8 Beca"!e of the reconver!ion

    of the !ol"#le compo"n$ to cell"lo!e; rayon i! referre$ to a! a regenerate$ cell"lo!e

    fi#er8

    There are !everal type! of rayon fi#er! in commercial "!e to$ay; name$ accor$ing

    to the proce!! #y which the cell"lo!e i! converte$ to the !ol"#le form an$ then

    regenerate$8 Rayon fi#er! are wet !p"n; which mean! that the filament! emerging

    from the !pinneret pa!! $irectly into chemical #ath! for !oli$ifying or regeneration8

    Gi!co!e rayon i! ma$e #y converting p"rifie$ cell"lo!e to =anthate; $i!!olving the

    =anthate in $il"te ca"!tic !o$a an$ then regenerating the cell"lo!e from the pro$"ct

    a! it emerge! from the !pinneret8 :o!t rayon i! ma$e #y the vi!co!e proce!!8

    5. 'i+/(+e #r(/e++

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    :o!t commercial rayon man"fact"ring to$ay "tili>e! the vi!co!e proce!!8 Thi!

     proce!! $ate! to the early 3)22!; with mo!t of the growth in pro$"ction occ"rring

     #etween 3)16 an$ 3)668 In the early perio$; pro$"ction wa! mainly te=tile

    filament; altho"gh the fir!t !taple wa! pro$"ce$ in 3)3'8 4igh performance rayon!;

    !"ch a! tire cor$; $i$ not appear "ntil the late 3)(2!; with the a$vent of hot-

    !tretching an$ a$$ition of larger amo"nt! of >inc to the !pin #ath8 Invention of 

    mo$ifier! in 3)5 #ro"ght on !"per tire cor$! an$ mar/e$ the #eginning of the

    high-performance rayon fi#er!8

    All of the early vi!co!e pro$"ction involve$ #atch proce!!ing8 In more recent

    time!; proce!!e! have #een mo$ifie$ to allow !ome !emi-contin"o"! pro$"ction8

    or ea!ier "n$er!tan$ing; the vi!co!e proce!! i! a #atch operation8 9lic/ on each

     proce!! !tep for a #rief e=planation8

    5.3 Cellul(+e

    P"rifie$ cell"lo!e for rayon pro$"ction "!"ally come! from !pecially proce!!e$

    woo$ p"lp8 It i! !ometime! referre$ to a! @$i!!olving cell"lo!e or @$i!!olving

     p"lp to $i!ting"i!h it from lower gra$e p"lp! "!e$ for paperma/ing an$ other 

     p"rpo!e!8 .i!!olving cell"lo!e i! characteri>e$ #y a high  -cell"lo!e content;i.e8;

    it i! compo!e$ of long-chain molec"le!; relatively free from lignin an$

    hemicell"lo!e!; or other !hort-chain car#ohy$rate!8

    ig81 9ell"lo!e

    5.4 Steepi)0

    The cell"lo!e !heet! are !at"rate$ with a !ol"tion of ca"!tic !o$a *or !o$i"m

    hy$ro=i$e+ an$ allowe$ to !teep for eno"gh time for the ca"!tic !ol"tion to

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     penetrate the cell"lo!e an$ convert !ome of it into @!o$a cell"lo!e; the !o$i"m !alt

    of cell"lo!e8 Thi! i! nece!!ary to facilitate controlle$ o=i$ation of the cell"lo!e

    chain! an$ the en!"ing reaction to form cell"lo!e =anthate8

     *9'432O6+n  nNaO4 *9'4)O5ONa+n  n41O

    5.5 #re++i)0

    The !o$a cell"lo!e i! !%"ee>e$ mechanically to remove e=ce!! ca"!tic !o$a

    !ol"tion8

    5.6 Shreddi)0

    The !o$a cell"lo!e i! mechanically !hre$$e$ to increa!e !"rface area an$ ma/e the

    cell"lo!e ea!ier to proce!!8 Thi! !hre$$e$ cell"lo!e i! often referre$ to a! @white

    cr"m#8

    5.7 A0i)0

    The white cr"m# i! allowe$ to !tan$ in contact with the o=ygen of the am#ient air8

    Beca"!e of the high al/alinity of white cr"m#; the cell"lo!e i! partially o=i$i>e$

    an$ $egra$e$ to lower molec"lar weight!8 Thi! $egra$ation m"!t #e caref"llycontrolle$ to pro$"ce chain length! !hort eno"gh to give managea#le vi!co!itie! in

    the !pinning !ol"tion; #"t !till long eno"gh to impart goo$ phy!ical propertie! to

    the fi#er pro$"ct8

    5.8 9a)thati()

    The properly age$ white cr"m# i! place$ into a ch"rn; or other mi=ing ve!!el; an$

    treate$ with ga!eo"! car#on $i!"lfi$e8 The !o$a cell"lo!e react! with the 9S1 to

    form =anthate e!ter gro"p!8 The car#on $i!"lfi$e al!o react! with the al/alineme$i"m to form inorganic imp"ritie! which give the cell"lo!e mi=t"re a

    characteri!tic yellow color , an$ thi! material i! referre$ to a! @yellow cr"m#8

    Beca"!e acce!!i#ility to the 9S1 i! greatly re!tricte$ in the cry!talline region! of 

    the !o$a cell"lo!e; the yellow cr"m# i! e!!entially a #loc/ copolymer of cell"lo!e

    an$ cell"lo!e =anthate8

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    *9'4)O5ONa+n  n9S1  *9'4)O5O-S9-SNa+n

    5.: Di++(lvi)0

    The yellow cr"m# i! $i!!olve$ in a%"eo"! ca"!tic !ol"tion8 The large =anthate

    !"#!tit"ent! on the cell"lo!e force the chain! apart; re$"cing the interchain

    hy$rogen #on$! an$ allowing water molec"le! to !olvate an$ !eparate the chain!;

    lea$ing to !ol"tion of the otherwi!e in!ol"#le cell"lo!e8 Beca"!e of the #loc/! of 

    "n-=anthate$ cell"lo!e in the cry!talline region!; the yellow cr"m# i! not

    completely !ol"#le at thi! !tage8 Beca"!e the cell"lo!e =anthate !ol"tion *or more

    acc"rately; !"!pen!ion+ ha! a very high vi!co!ity; it ha! #een terme$ @vi!co!e8

    5.; Ripe)i)0

    The vi!co!e i! allowe$ to !tan$ for a perio$ of time to @ripen8 Two important

     proce!!e! occ"r $"ring ripening Re$i!tri#"tion an$ lo!! of =anthate gro"p!8 The

    rever!i#le =anthation reaction allow! !ome of the =anthate gro"p! to revert tocell"lo!ic hy$ro=yl! an$ free 9S18 Thi! free 9S1 can then e!cape or react with

    other hy$ro=yl on other portion! of the cell"lo!e chain8 In thi! way; the or$ere$; or 

    cry!talline; region! are gra$"ally #ro/en $own an$ more complete !ol"tion i!

    achieve$8 The 9S1 that i! lo!t re$"ce! the !ol"#ility of the cell"lo!e an$ facilitate!

    regeneration of the cell"lo!e after it i! forme$ into a filament8

    *9'4)O5O-S9-SNa+n  n41O *9'432O6+n  n9S1  nNaO4

    5.< Filteri)0

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    The vi!co!e i! filtere$ to remove "n$i!!olve$ material! that might $i!r"pt the

    !pinning proce!! or ca"!e $efect! in the rayon filament8

    5.3= De0a++i)0

    B"##le! of air entrappe$ in the vi!co!e m"!t #e remove$ prior to e=tr"!ion or they

    wo"l$ ca"!e voi$!; or wea/ !pot!; in the fine rayon filament!8

    5.33 Spi))i)0 *Ket Spinning+

    The vi!co!e i! force$ thro"gh a !pinneret; a $evice re!em#ling a !hower hea$ with

    many !mall hole!8 Each hole pro$"ce! a fine filament of vi!co!e8 A! the vi!co!e

    e=it! the !pinneret; it come! in contact with a !ol"tion of !"lf"ric aci$; !o$i"m

    !"lfate an$; "!"ally; Zn ion!8 Several proce!!e! occ"r at thi! point which ca"!e

    the cell"lo!e to #e regenerate$ an$ precipitate from !ol"tion8 Kater $iff"!e! o"t

    from the e=tr"$e$ vi!co!e to increa!e the concentration in the filament #eyon$ the

    limit of !ol"#ility8 The =anthate gro"p! form comple=e! with the Zn  which $raw

    the cell"lo!e chain! together8 The aci$ic !pin #ath convert! the =anthate f"nction!

    into "n!ta#le =antheic aci$ gro"p!; which !pontaneo"!ly lo!e 9S1 an$ regenerate

    the free hy$ro=yl! of cell"lo!e8 *Thi! i! !imilar to the well-/nown reaction of 

    car#onate !alt! with aci$ to form "n!ta#le car#onic aci$; which lo!e! 9O1+8 There!"lt i! the formation of fine filament! of cell"lo!e; or rayon8

     *9'4)O5O-S9-SNa+n  Cn41SO5  *9'432O6+n  n9S1  CnNa1SO5

    5.34 Dra>i)0

    The rayon filament! are !tretche$ while the cell"lo!e chain! are !till relatively

    mo#ile8 Thi! ca"!e! the chain! to !tretch o"t an$ orient along the fi#er a=i!8 A! the

    chain! #ecome more parallel; interchain hy$rogen #on$! form; giving the filament!the propertie! nece!!ary for "!e a! te=tile fi#er!8

    5.35 Wa+hi)0

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    The fre!hly regenerate$ rayon contain! many !alt! an$ other water !ol"#le

    imp"ritie! which nee$ to #e remove$8 Several $ifferent wa!hing techni%"e! may #e

    "!e$8

    5.36 Cutti)0

    If the rayon i! to #e "!e$ a! !taple * i.e.; $i!creet length! of fi#er+; the gro"p of 

    filament! *terme$ @tow+ i! pa!!e$ thro"gh a rotary c"tter to provi$e a fi#er which

    can #e proce!!e$ in m"ch the !ame way a! cotton8

    ig8( 9hemical Reaction involve$ in GS Proce!!

    6. ET# pre+e)t +tatu+

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    Effl"ent! get generate$ in the proce!! at !everal point! an$ can #e cla!!ifie$ "n$er 

    three #roa$ hea$!; i8e8 al/aline; aci$ic an$ ne"tral8 The ma?or !o"rce! of 

    wa!tewater generation from plant incl"$e proce!!; cooling; #oiler fee$; cleaning;

    floor wa!hing an$ $ome!tic $i!charge!8 Total wa!tewater generate$ from all the

    a#ove !o"rce! for e=i!ting pro$"ction i! 16;222 mQF$8 The contaminant! from thevario"! !o"rce! "n$ergo change! when the effl"ent !tream! merge with one

    another8 The merger of aci$ic an$ al/aline effl"ent! re!"lt! in partial ne"trali>ation

    of aci$ity8 9ell"lo!e pre!ent in a $i!!olve$ !tate in the al/aline effl"ent i!

    regenerate$ an$ remain! a! !"!pen$e$ matter in the a#ove effl"ent8 The "nit ha!

    in!talle$ a f"ll-fle$ge$ Effl"ent Treatment Plant *ETP+ #a!e$ on primary treatment

    of ne"trali>ation an$ clarification followe$ #y !econ$ary treatment $e!igne$ on the

     principle of e=ten$e$ aeration activate$ !l"$ge proce!!8 Thi! i! !"pplemente$ with

    a ca!ca$e aerator an$ a poli!hing pon$8 The effl"ent generate$ from $ifferent!tream! i8e8 aci$ic; al/aline an$ ne"tral !tream i! ta/en to the e%"ali>ation tan/ 

    thro"gh preliminary treatment8

    6.3 E?uali@ati() Ta)

    9om#ine effl"ent from preliminary treatment i! ta/en to the e%"ali>ation tan/ of 

    $iameter 3(86 m an$ !i$e water $epth (82 m8 :ain p"rpo!e of e%"ali>ation i! to

    ta/e care of variation in flow an$ characteri!tic! of $ifferent !tream! #y mi=ing the

    effl"ent!8 The e%"ali>e$ flow i! ta/en to the ne"trali>ation tan/8

    6.4 Neutrali@ati() Ta)

    The e%"ali>e$ flow i! ne"trali>e$ in thi! tan/8 A tan/ of $iameter 3'8J m an$ !i$e

    water $epth 18( m i! "!e$ for thi! p"rpo!e where a$e%"ate %"antity of lime i!

    a$$e$8 .o>ing of -32 M lime !l"rry i! reg"late$ to maintain p4 of 82 to 868

    9alci"m !"lphate form! in accor$ance with the following reaction

    41SO5  9a *O4+ 1 9aSO5  141O

    The !l"rry containing precipitate$ calci"m !"lphate goe! to !l"$ge Thic/ener an$

    i! then mi=e$ with !l"$ge of Primary clarifier8 The overflow i! ta/en to the primary

    clarifier for f"rther treatment8

    6.5 #rimar2 Clari*ier

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    Two n"m#er! of primary clarifier! are in!talle$ for primary treatment8 The flow

    from ne"trali>ation tan/ i! ta/en to the primary clarifier 3 for removal of !ettla#le

    !oli$!8 The $iameter of primary clarifier 3 i! (586 m an$ !i$e water $epth i! (85 m8

    The !l"$ge !ettle$ at the #ottom of the tan/ i! contin"o"!ly ta/en to !l"$ge

    thic/ener for thic/ening with the help of !crapper!8 Scrapper! p"!h the !l"$gealong the tan/ #ottom to collecting channel8 Primary clarifier 1 i! /ept a! a !tan$#y

    "nit8 The overflow from primary clarifier n"m#er 3 i! ta/en for a com#ine$

     #iological treatment after a$$ition of "rea an$ .AP a! n"trient! for the meta#olic

    activitie! of the micro-organi!m!8

    6.6 Aerati() Ta)

    Biological treatment a$opte$ i! activate$ !l"$ge proce!! with e=ten$e$ aeration

    !y!tem compri!ing of an aeration tan/ of !i>e J'82 m = 56 m = ( m having thirteenn"m#er! of 12 hp an$ nine n"m#er! of 52 hp !"rface aerator!8 Ka!tewater with p4

    val"e aro"n$ 82 having n"trient! in the ratio of BO. N P *32263+ i! fe$ to

    aeration tan/8 Re%"ire$ concentration of @:i=e$

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    Settle$ !l"$ge from primary an$ !econ$ary clarifier i! ta/en to the !l"$ge thic/ener 

    for re$"ction of vol"me8 Thi! !l"$ge generate$ i! con!i!ting mainly of cell"lo!ic

    matter an$ contain! heat potential8 The thic/ene$ !l"$ge i! tran!ferre$ to the #elt

     pre!! for f"rther $ewatering8

    6.: Belt #re++

    The!e are the !l"$ge $ewatering $evice! that involve the application of chemical

    con$itioning; gravity $rainage an$ mechanically applie$ pre!!"re to $ewater the

    !l"$ge8

    9on$itione$ !l"$ge i! fir!t intro$"ce$ on a gravity $rainage !ection where it i!

    allowe$ to thic/en8 ollowing the gravity $rainage; pre!!"re i! applie$ in a low-

     pre!!"re !ection; where the !l"$ge i! !%"ee>e$ #etween oppo!ing poro"! cloth

     #elt!8 The final $ewatere$ !l"$ge ca/e i! remove$ from the #elt! #y !craper #la$e!8

    Two "nit! of #elt pre!! are provi$e$ in the ETP8

    6.; Wa+te>ater Di+p(+al

    The Treatment Plant i! f"nctioning on contin"o"! #a!i!8 The %"antity of the

    effl"ent treate$ in the Effl"ent Treatment Plant for e=i!ting pro$"ction i!

    16222mQF$8 after en!"ring the %"ality of water it i! relea!e$ in the 9ham#al River8

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    ig85 low $iagram of ETP

    7. #r(p(+ed ) te/h)(l(02

    There i! the compari!on #etween the two chemical al"m an$ >inc "!e$ in

    man"fact"ring vi!co!e rayon

    Al"m ZincEco-frien$ly 4a>ar$o"!

    cheap 9o!tly

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    ig86 9ro!! !ectional view of the fi#er! of al"m proce!!

    ig8' 9ro!! !ection view of the fi#er of >inc proce!!

    8. R(le (* @i)/ i) +pi))i)0 pr(/e++

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    The !e%"ence of phy!ical an$ chemical tran!formation! ta/ing place at !pinning

    i! e=tremely comple= an$ !till not f"lly characteri>e$8 The main reaction i! clearly

    reformation of cell"lo!e from !o$i"m cell"lo!e =anthate #y the action of !"lph"ric

    aci$;

    1 cell"lo!e,O 9S1 Na 41SO5 1 cell"lo!e,O4 Na1SO5 19S1

    4owever; thi! follow! the tran!ient formation of the more !ta#le >inc cell"lo!e

    =anthate in certain region!; with a$$itional more comple= !pecie! al!o #eing

    forme$ if vi!co!e mo$ifier! are "!e$8 Zinc !"lphate i! !ol"#le "p to aro"n$ p4 J86;

    !o thi! material penetrate! into the forming filament! ahea$ of ne"trali>ation

    *reaction (85 a#ove+8 4owever; after the initial formation of >inc cell"lo!e =anthate

    *followe$ rapi$ly #y regeneration to cell"lo!e+ in the o"ter region! of the filament!;

    f"rther penetration i! #elieve$ to #e impe$e$ #y the formation of other >inc !pecie!

    !"ch a! Zn*O4+1 an$ ZnS8 4ence the formation of a tran!ient region of >inc

    cell"lo!e =anthate i! overta/enL #y the penetration of aci$8

    The region in which >inc cell"lo!e =anthate ha! forme$ i! #elieve$ to #e

    re!pon!i#le for the !/in effect which can #e !een in rayon fi#re cro!!-!ection!8

    The !/in region retain! $ye #eca"!e of a greater $egree of cry!tal !tr"ct"re relative

    to the core8 The tran!ient >inc comple= i! #elieve$ to ai$ the formation of greater 

    cry!tallinity #y $elaying regeneration relative to !o$i"m cell"lo!e =anthate *the

    >inc variant i! more !ta#le+; an$ po!!i#ly al!o #y cro!!-lin/ing #etween

    neigh#oring cell"lo!e chain!; allowing greater orientation to #e achieve$8

    Beca"!e of the effect of >inc on cry!tallinity; which "ltimately tran!late! to

    improve$ ten!ile !trength; the pro$"ction of high !trength rayon "!"ally involve!

    high level! of >inc in the !pin#ath8 :o!t plant! "!e #etween 286 an$ 386M >inc

    !"lphate in the !pin#ath for reg"lar !taple pro$"ction8 Below 286M; a !ignificant

    $eterioration in fi#re ten!ile re!"lt! which can to !ome e=tent #e recovere$ #y

    rai!ing !o$i"m !"lphate concentration an$ re$"cing the aci$ concentration8 At very

    low level! of >inc in the !pin#ath; the filament cro!!-!ection #ecome! very

    irreg"lar; with only a !mall amo"nt of !/in #eing apparent8

    :. Literature +urve2

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    The ."tch 4olima proce!! precipitate! the >inc a! the car#onate on inert n"clei

    which can #e !creene$ off an$ $i!car$e$8 A patent $e!cri#e! the "!e of !o$i"m

    car#onate or #icar#onate to precipitate >inc car#onate8 It i! recommen$e$ for 

    vi!co!e rayon !ol"tion! in which the ratio of the weight percentage! of >inc an$

    !"lph"ric aci$ i! at lea!t 3(8

    Precipitation of the >inc "!ing lime i! well /nown an$ ha! #een "!e$ in plant !cale

    for year! in E"rope an$ the 78S8 B"t; a $en!e; recovera#le >inc precipitate ha!

    never #een mentione$8 7!"ally; com#ine$ plant wa!te! are treate$ with lime; an$

    the re!"lting !l"$ge containing >inc; calci"m; cell"lo!e; etc8; i! $i!car$e$ to

    lagoon!8

    Ion e=change proce!!e! appear fre%"ently in the literat"re8 Some of their $i!a$vantage! are

    38 The effl"ent; !till highly aci$; ha! to #e ne"trali>e$ anyway #efore $i!charge8

    18 Aci$ an$ !o$i"m ion! compete for the a$!orption of >inc on the re!in;

    re$"cing it! capacity a! m"ch a! 62M when the !o$i"m an$ hy$rogen ion!

    amo"nt to 36 gram!Fliter8 A !pill of concentrate$ aci$ #ath m"!t #e collecte$ an$

    $il"te$ with !oft water #efore it reache! the re!in8

    (8 9ertain amine! an$ !pinning agent! poi!on the re!in an$ re$"ce it! capacity8

    58 Efficient a$!orption of imp"ritie! !"ch a! calci"m; magne!i"m; iron; lea$;

    copper; etc8; often prevent re"!e of the >inc witho"t f"rther chemical !eparation!8

    68 The efficiency of >inc removal i! low8 By "!ing a recycle re-generation !y!tem;

    the efficiency of recovery will average )1M8

    A R"!!ian proce!! may #e mentione$8 It precipitate! an$ $i!car$! the >inc a! >inc

    !"lfi$e #y "!ing hy$rogen !"lfi$e from the wa!te rayon !pinning ga!e!8

    A &erman proce!! "!e! an activate$ !l"$ge !y!tem to re$"ce the >inc content of 

    wa!te water! to ' - 32 mg8 Fl8 It wa! more effective in har$ water!8 The >inc i!

    $i!car$e$ together with the #iological !l"$ge8

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    An$; of co"r!e; if the concentration of >inc an$ other chemical! warrant! it; the

    aci$ wa!te !ol"tion! can #e concentrate$ #y evaporation an$ then re"!e$8 or 

    !team economy; m"ltiple effect evaporator! are prefera#ly employe$8

    ;. Re/(ver2 +2+tem (* i)/

    Zinc i! "!e$ a! regeneration retar$ant in the aci$ !pinning #ath8 Beca"!e it i! not

    con!"me$ in any of the vi!co!e reaction!; the "!e$ >inc repre!ent proce!! lo!!e!;

    thro"gh $rag o"t #y the filament! to the !"#!e%"ent wa!h !tream!; filter 

     #ac/wa!hing; !pla!he!; lea/!; an$ the wa!hing of e%"ipment8 The effect! of >inc a!

    a poll"tant are well $oc"mente$8 9oncentration! a! low a! 382 mgF< have #een

    !hown to #e harmf"l to fi!h8 In a$$ition; there i! !ome evi$ence in$icating that >inc

    ha! a !ynergi!tic property when a!!ociate$ with copper8

    Altho"gh it ha! #een /nown that >inc can #e precipitate$ from aci$ wa!te !tream!

     #y the "!e of lime; the re!"ltant !l"$ge ha! #een of low >inc a!!ay; contaminate$

    with other compo"n$!; an$ with very poor !ettling characteri!tic!8 In commercial

    operation!; the !l"$ge pre!ente$ a $i!po!al pro#lem an$ recovery of >inc !"ita#le

    for recycle wa! impo!!i#le8

    The >inc in the !l"$ge wa! recovere$ an$ recycle$ to the rayon man"fact"ring

     plant8 Thi! recycling of >inc wa! !hown to have no ill effect! on the rayon yarn8

    Thi! proce!! greatly enhance! the economic! of removing thi! !o"rce of >inc

     poll"tion; allowing ne"trali>ation of the aci$ !tream an$ recovery of the >inc while

    generating a goo$ profit for in$"!trial yarn! an$ at a mo$erate co!t for te=tile

    yarn!8

    #r(/e++

    The /ey to thi! >inc recovery proce!! i! a two-!tage precipitation; with the !econ$ precipitation ta/ing place "n$er caref"l p4 control; "!ing !o$i"m hy$ro=i$e in

    contact with circ"lating !l"rry of >inc hy$ro=i$e cry!tal!8 All of the >inc

     precipitate! in the !econ$ !tep; mo!t of the imp"ritie! in the fir!t8 The element! of 

    the proce!! are a! follow!8 Aci$ an$ al/aline wa!te !tream! are collecte$ in a

    ne"trali>ation tan/8 4ere !"fficient lime i! a$$e$ to rai!e the p4 to '828 At thi!

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     point; no >inc hy$ro=i$e will precipitate #"t a portion of the iron; calci"m !"lfate;

    an$ other imp"ritie! will form a light precipitate8 Kith a coag"lant ai$; the mi=t"re

    i! !ent to a clarifier where a clear overflow containing the $i!!olve$ >inc i!

    o#taine$8

    Thi! clear overflow i! contacte$ in a reactor with a circ"lating !tream of previo"!ly

     precipitate$ !l"$ge containing >inc hy$ro=i$e8 The p4 i! rai!e$ !"#!e%"ently to )86

    to 3282 with !o$i"m hy$ro=i$e8

    The #"l/ of the >inc precipitate! onto the e=i!ting cry!tal! in the circ"lating !l"rry8

    At !tea$y-!tate con$ition!; the with$rawal rate of the circ"lating !l"rry !tream i!

    ma$e e%"ivalent to that of the >inc #eing a$$e$8 Thi! $en!e !l"$ge i! then !ettle$8

    The !ettle$ !l"$ge of 5 to M >inc a!!ay i! converte$ #ac/ to >inc !"lfate with

    !"lf"ric aci$ an$ !ent #ac/ to the !pinning #ath8 If $e!ire$; the !l"$ge can #efiltere$ or centrif"ge$ to 3JM !oli$! #efore $i!!olving with aci$8

    The >inc content of the overflow water from the $en!ator-reactor i! !et #y the p4, 

    !ol"#ility relation!hip of >inc in water an$ re!"lt! in >inc content of 286 to 3 mgF<

    at p4 328 Once the precipitate$ >inc i! remove$ from the wa!tewater; the p4 can

     #e rea$?"!te$ to a lower val"e8

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    ig8 .en!ator 

    3=. The E/()(mi/+

    The conventional techni%"e for removing >inc from the !pinning aci$ wa!te !tream

    ha! #een $irect lime precipitation to Up4 32; with no >inc recovery8 The economic!

    of recovery are a very !trong f"nction of the amo"nt of >inc "!e$ in the preparation

    of the yarn an$ the ratio of aci$ to >inc in the !pinning #ath8 In man"fact"ring

    in$"!trial yarn! an$ tire cor$!; it i! common to "!e 586 to 86 /g of >inc per 322 /g

    of yarn8 Thi! high concentration of >inc ma/e! recovery e=tremely attractive8

    Te=tile yarn! "!e le!! >inc; an$ altho"gh recovery i! !till the mo!t economic

    !ol"tion; it offer! le!! of a ret"rn8 The!e two ca!e! are pre!ente$ a! e=treme!; with

    many plant! falling #etween the two val"e!8

    33. Area+ (* Appli/ati()

    Thi! technology; with only !mall mo$ification! to conform to local plant

    con$ition!; co"l$ have imme$iate application in any vi!co!e rayon plant with

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    The concentration of >inc in !pin#ath i! aro"n$ 5622ppm8 After the generation of 

    fi#er !ome amo"nt of >inc carryover to ne=t !tage with fi#er8 rom the e=periment

    it !how! it i! 62ppm that come! in ETP after fir!t wa!h8

    or 3 ton of fi#er; it re%"ire 32 m

    (

     water for wa!hing

    or 522 ton of fi#er; it re%"ire 5222 m( water for wa!hing

    That 5222 m( effl"ent come in ETP that contain 62ppm >inc a! >inc !"lphate

    Amo"nt of >inc

    5222=62122222 gm Zn 122/g Zn a! ZnSO5F$ay

    The main reaction

    ZnSO5  1NaO4 Zn *O4+1 Na1SO5

    The reaction !how! that J2gm of NaO4 re%"ire reacting with 3'385gm of ZnSO5

    in that >inc i! '68(Jgm; to give ))8(Jgm of Zn *O4+1 a! precipitate 8

    or 122/g Zinc or 5)(8)5/g ZnSO5  it re%"ire! 15685(J/g of NaO4 to give

    (2582'J/g of Zn *O4+1 a! precipitate8

    If the efficiency of that proce!! i! )2M mean! 12/g or 6ppm >inc will #e there after 

    treatment; that will #e $il"te$ to 6 time! *3ppm+ after mi=ing with other !tream of 12222m(F$ay

    The efficiency of the >inc recovery proce!! $epen$! on the concentration of the

    !ol"#le >inc in the aci$ fee$8 Thi! i! $"e to the fact that "nle!! there i! an

    a#normality in the .en!ator operation; !"ch a! an acci$ental low p4; the !ol"#le

    >inc in the clear effl"ent remain! e!!entially con!tant8 Therefore; the higher the

    !ol"#le >inc concentration in the fee$; the higher the percent efficiency of >inc

    recovery8

    35. ET# AFTER MODIFICATION

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    ig8) mo$ifie$ ETP

    36. EFFLENT WATER ALIT"

    The effl"ent water i! normally very clear8 It $oe! contain a#o"t 1;222 - 1;622 ppm

    of $i!!olve$ !o$i"m !"lfate; which i! pre!ent in the fee$ to the plant; an$

    !omewhat le!! than 1;222 ppm of $i!!olve$ calci"m !"lfate; cor- re!pon$ing to the

    !ol"#ility of gyp!"m in the pre!ence of thi! amo"nt of !o$i"m !"lfate8 Thi! water i!

    !"ita#le for re"!e wherever the high !"lfate an$ high har$ne!! i! not an

    impe$iment for e=ample; a! cleaning an$ fl"!hing water; p"mp !eal water; etc8 It

    ha! #een "!e$ for all water nee$! in the >inc recovery plant e=cept for lime !la/ing

    an$ $il"ting water; an$ for the !afety !hower an$ eye wa!h !tation8

    Any "n"!e$ effl"ent water !ho"l$ #e mi=e$ with other plant effl"ent! to re$"ce it!

     p4 of )86 - 3282; or aci$ifie$ in !ome ine=pen!ive way8

    37. RESE OF INC

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    The recovere$ >inc ha! #een "!e$ for many month! in the rayon plant8 Beca"!e the

    >inc contain! !ome magne!i"m; it i! "!e$ in a rayon #ath that contain! #oth >inc

    an$ magne!i"m8 Thi! #ath i! the !ame one that contri#"te! the magne!i"m to the

    recovery plant fee$8

    38. OT!ER #ROCESSES

    38.3 S(lve)t e1tra/ti() pr(/e++

    Recovery of >inc from the effl"ent ha! !"cce!!f"lly #een accompli!he$ "!ing

    !olvent e=traction8 In the proce!!; >inc i! e=tracte$ to more than )6M *p41+ with

    $i-ethyl he=yl pho!phoric aci$ *.E4PA+ $i!!olve$ in /ero!ene in two or three

    !tage!8 Stripping i! performe$ with a !"lph"ric aci$ !ol"tion8 By a$?"!ting the net

    flow rate of the !trip !ol"tion; the concentration of >inc in !ol"tion may #eincrea!e$ to 62 gFl or more8 Th"!; the re!"lting >inc !"lphate !ol"tion can #e re-

    "!e$ $irectly in the !pinning #ath8

    ig832 E=traction of Zinc from wea/ aci$ effl"ent!

    38.4 Re/(ver2 (* @i)/ u+i)0 thi(ph(+phi)i/ e1tra/ta)t

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    A proce!! ha! #een $evelope$ for the recovery of >inc from rayon wa!te effl"ent

    following !olvent e=traction techni%"e "!ing thiopho!phinic e=tractant! 9yane=

    11 an$ (218 Before recycling of >inc !"lphate !ol"tion in !pinning #ath; !ol"tion

    m"!t #e free from calci"m; which i! $eleterio"! to the proce!! a! gyp!"m

     precipitate! an$ form! !cale8 The e=tractant 9yane= (21 ha! #een fo"n$ !elective

    for the recovery of ))8))M of >inc in the form of [R 1Zn org from the effl"ent a#ove

    e%"ili#ri"m p4 (85 maintaining the OFA ratio of 3F(2 leaving all the calci"m in the

    raffinate8 The >inc from the loa$e$ 9yane= (21 can #e !trippe$ with 32M !"lph"ric

    aci$ at even OFA ratio of 328 The !trippe$ !ol"tion th"! o#taine$ co"l$ #e recycle$

    in the !pinning #ath of the rayon plant an$ raffinate co"l$ #e $i!po!e$ !afely

    witho"t affecting environment

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    3:. #ROCEDRE FOR T!E DETERMINATION OF ACID INC AND

    MAGNESIM IN WASTE WATER 

    A9I.

    :ea!"re 322 ml8 of !ample into a 162 ml8 Erlentneyer fla!/; a$$ ( or $rop! of 

    (6M hy$rogen pero=i$e; an$ let !tan$ for ( or 5 min"te!8 A$$ 1 or ( $rop! of 

    :ethyl Re$ in$icator; an$ titrate with NF32 NaO48

      9alc"lation Titration = 283 = 2825) = 322F322 M41SO5 

    ZIN9

    A$$ 32 ml8 of maleic aci$ - !o$i"m maleate #"ffer !ol"tion *p4 '8J+; an$ 5 to J

    $rop! of Eriochrome Blac/ T in$icator to the titrate$ !ol"tion "!e$ for aci$

    $etermination8 Titrate with 2821 $i!o$i"m ver!enate !ol"tion to a color change

    8from p"rple-re$ to p"rple-#l"e8  9alc"lation Titration = '86 p8 p8m8 a! Zn8

    :A&NESI7:

    A$$ 36 ml8 of ammonia - ammoni"m chlori$e #"ffer !ol"tion *p4 322+ to the

    titrate$ !ol"tion from the aci$ an$ >inc $etermination!8 Titrate with 2821 N

    $i!o$i"m ver!enate !ol"tion! to appro=imately J2M of the e=pecte$ titration8 A$$

    1 to 5 $rop! of Eriochrome Blac/ T in$icator an$ contin"e the titration to a !/y-

     #l"e color 

      9alc"lation Titration = 185 p8p8m8 a! :g8

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    3;. C()/lu+i()

    The following concl"!ion! can #e $rawn from thi! !t"$y

    • The efficient an$ economical recovery an$ re"!e of wa!te !ol"#le >inc from

    vi!co!e rayon plant wa!te! ha! #een proven "n$er in$"!trial con$ition!

    The efficiency of the precipitation an$ recovery of !ol"#le >inc e=cee$!)6M; which i! higher than that of other /nown metho$! !"ch a! ion

    e=change8

    • The effl"ent water from the recovery plant i! e=tremely clear water of 

    con!tant; !lightly al/aline p4 an$ it i! e!!entially free of to=ic metal content8

    •  It can #e re"!e$ to a$vantage where it! high har$ne!! an$ !alt content i! not

    an impe$iment; !"ch a! water for fl"!hing an$ cleaning p"rpo!e!; p"mp !eal

    water; etc8 It! !ol"#le >inc content i! le!! than 1 ppm8

    3inc an$ !eparation of calci"m "!ingthiopho!phinic e=tractant :808 Dha G8 0"mar; .8 Bagchi; R8D8 Singh; Dae-ch"n