cu») United States 2) Patent Applicat EKKELENKAMP et al. n Publica (54) PROCESS FOR PRODUCING AMMONIUM SULFATE CRYSTALS (71) Applicant: DSM IP ASSETS B.., TE Heerlen ry (72) Inventors: Geert EKKELENKAMP. Heerlen (NL): Johannes Elisabeth Pierre DEBE, Heerlen (NL); Robert GEERTMAN, Heerlen (NL); Peter YAN YSACKER, Heerlen (NL); Johan ‘Thomas TINGE, Heerlen (NL) (21) Appl. Nos 14/649,823 (22) PCTFiled: Now. 29, 2013, (86) PCTNo: — POTBP2013/075087 S371 (Oil), (2)Dae: "Jun. 4, 2018 G0) Forcign Application Priority Data Dec. 6.2012 (EP) 121958128 US 2016/0214868 Al Jul. 28, 2016 US 2016021486841 (10) Pub. No. (43) Pub, Dat Publication Classification (1) Ince Coie 124 200601) BoD 9700 (2006.01) (2) US.CL COIC 124 (2013.01); BOID 90031 (2013.01); BorD 900d (2013.01); BOD ‘70039 (2013.01); BOLD 2009/0086 201301) 6 ABSTRACT The present vention provides a continuous process foe pro ducing, ammonium sulfate crystals, wherein said process ‘comprises: i) feeding tow series of crystallization sections, ‘whieh erystalization sections are heat integrated in series, solution of ammonium sulfate; i) crystallizing ammonivzn sulfate crystals from said solution of ammonium sist; i) purging. Traction ofthe solution of ammonium sulfate rom fch of said erystalization scctionssand iv) discharging ‘ammonium sulfate crystals from each erstallization section, characterized in that: fraction of sad softion of ammonitim sulfates punzed from atleast one erytallizatio section oat Teast one other erytallization section; and an appara sut- able for producing ammonium sulfate erysas. (6) 7) —| te) (9) (20) (a) (2) (3) (4) > | oy | oe (11) (13) dom (15) (17)Patent Application Publication _ Jul. 28, 2016 Sheet 1 of 2 US 2016/0214868 AI (20) > I o (14) i} A J a (11) (13) (15) (a7)Patent Application Publication Jul. 28, 2016 Sheet 2 of 2 US 2016/0214868 AI (10) >US 2016/0214868 AI PROCESS FOR PRODUCING AMMONIUM SULFATE CRYSTALS [0001] The invention relates to a process for preparing ammonium sulfate erystals [0002] Ammonium sulfate is useful as a fertilize, eg, for tse in agriculture, horticulture or foresty. Is ofen applied ‘asa crystalline material. Ammonium sulfate crystals foe this tise are classified according to crystal size. In general lange ‘eystals are more easy to handle. Further crystals ofa cet size distribution, of relatively large average crystal size, can be used in commercially valuable fertilizer blends and are therefore economically more valuable than small crystals However, it is desirable to produce ammonium sulfate of different grads, for different applications 10003] Ammonium sulfate crystals may be obtained by subjecting an ammonium sulfate solution to exystallization ‘and subjecting the resuling slurry of ammonium sulfate erys- tals toa size classification step. The lange crystals are gener ally desired asthe product fora further use in particular for use aw fetlizer 0003) Crystallization by evaporation typically involves hat input o evaporate solvent aad concentrate the remaining solution, In onder to reduce steam consumption nooded for ‘ceaporative erstallization in the prediction of sodium chlo- ride crystals from aqueous sodium chloride solutions, for ‘example, a series of erystallizers are in general integrated with respect to heat input (see eg. I. Krstansson, Geother- mies, 21 (1992): pp 765-771). This is commonly done by passing steam at «high temperature into the firs rystallizer fn aseries, The esulling lower temperature steam is used 10 heat the next crystallize, and so on, This means that a series ‘oferystallizers operates at descending temperatures, The size and conditions ofthe erystallizers are optimized fortis heat ing arrangement, GB748572 describes process for the multi-stage evaporation of salt depositing liquids, in onder to ‘void fouling, However, no specifie products deseribed other than salt solution or celtulose waste liquor 10005] | W020001077346 deseribes a process for separating fines of ammonium sulfate from a suspension of erystals of ‘desired size by use ofa wash thickener. Solution from which the crystals are separate is used i the wash thickener 10006] During conventional operation of an evaporative ‘eqstllizer, impurities become concentrated inthe solution, ‘Accordingly, purue is employed, whereby solution is, con- tinuously or periodically, discharged from the crystallize. ln ‘a conventional series of erytallization sections, each erystal- ization section operates atthe same concentration of impu- iy. Since the impurity of the erytals produced is propor tional ta the purity of the solution from which they ae groken, the product crystals fom each crystallization seetion in the series contain the same level of impurity [0007] | DE4314281C1 describes a multi-stage evaporation ‘of aqueous ammonium sulfate solutions from caprolactam, production involving rcirelation of the mother liquor. [0008] However, itis desirable t produce higher purity rides of crystalline product for different application Higher purity product is economically more valuable. The present inventors have found method of inereasing the purity ofthe majority of erystal produced by a crystallization section, Specifically, they have found that by introdvcing @ system where ammonium sulfate solution i purged from one ‘eystllization section in the series to another erytallization sccton in the series, the mcan concentration of impurities ia the series of erystallizaton sections can be reduced. Further, Jul. 28, 2016 the system of pursing can be arranged such thatthe purity of pradhct crystals rom all but one of the crystallization sec- ‘ions is far higher than that ofthe prior at. Aa additional ‘advantage ofthe invention is thatthe erystallizaton yield of ‘ammonium sulfate eeystas with a high purty is higher than that ofthe prior ar. And further, the advantages mentioned before ean be combined. 0009} Accordingly, the present invention provides a con- tinuous process for producing ammonium sulfate crystals, ‘wherein sid process comprises [010] i) feeding to a series of crystallization sections, ‘which crystallization soctions are heat integrated in Series solution of ammonium sulfite: 0011] i) crystallizing ammonium sulfate crystals from said solution of ammonium sulfate 10012] it) purging a fraction of the sotution of ammo- nium sulfate from each of said crystallization sections; [0013] iv) discharging ammonium sulfate crystals from ‘ach crystallization section, characterized in that [0014] a fraction of ssid solution of ammonium sulfate is purged fromat least one crystallization section tat least ‘one other crystallization section [0015] The present invention futher provides appaatus suitable for producing ammonium sulfate erystals, compis- ing: [0016] i) a series of erystallization sections of substan- tially equal produetion capacity of ammonium sulfate crystals, which are configured tobe heat integrated with respect to steam; [0017] iia steam supply system integrating the erystal- lization sections in series 0018] ii) feed of ammonium sulfate Solution; and [0019] iv) a system of removal of ammonium sulfate eystals 0020] characterized in that, [021] stleastoncerystalization section sconneeted by 4 purge line 10 another erystlizaton setion inthe (0022) As wsod herein, ammonium sulfite enya include Smpurties that may’ be present, as Known by the skilled per {0028} A crystalizaton section comprises ll equipment ooessary to accep a soation of ammoniam sles, and Giseharge ammonium solfae eras. In is simplest form this means a crystallize anda separation unit [0024] A sexes of erystlization sections, which erstall- ‘atin seston are et intext series means that heat is ‘plied w the crystallization setion atone en of te series haat is then transfered, dvety oF indirety 10 the next crystallization section in the series: and so on ntl the last eystalization section inthe serie. In this way, a single extemal heat source is used oat al crystallization units ia tne series, buts applied telly only tthe irs (0025) By purging ration ofthe solution of ammonia sulfates meant that faction ofthe solution of ammonia sulfate is discharge foo the crystalization section, The purpose ofthe purge isto redvce the impurity content inthe Solation of sitimonium sullte, thereby also redacing the ‘parity content ofthe crystal ammonium slit. (0026) A soltion of ammonium solfte consists just of Solvent, impurities and (pure) ammoninm sulfate. Ammo- ham ie esas oi ot of mpc a)US 2016/0214868 AI 10027] The separetion fietor is the ratio between the mount of impurities in the solution of ammonium salfate (mother liquor and the amount of impurities incorporated ia the ammonium sulfate crystals formed from suid solution. Both are measured on @ muss basis. Separation factor, S, is defined $f, gM a ag 5 where 10028] mq,""@"-mass impurities in 1 kg solution of namonin sulfate 10029] Mhjan!*"-mass pure ammonium sulfate in Le solution oF ammonium sulfate 10030] Mjgg"""-mass impurities in 1 ammonia sl fate erystals 10031] Mhjgn mass pure ammonium sulfate in 1 ke saamonium sulfate crystal 0032] Forexample, fora system with assparationfactorof 1000, the impurity content ofthe erytals i 0.1% that ofthe Jampurty content of the solution fom which the erystals are {ormed, During evaporative crystalization, the impurity con- tent ofthe solution therefore increases. The purge s used t0 sischarge solution witha high impurity content. Purging may’ be continuous or intermittent. 10083] “The apparatus ofthe present invention comprises ‘egatallization sections which ae configured tobe heat inte- jrted with respect to steam. By ths its meant that team is the heat source, and thatthe series of erytallizaton sections ‘comprises the necessary pipework thatheat ean be transferred by input of steam to the est crystallization setion in the series and the heat transfered oghout the series as described above. The temperature of successive emstaliza- tion sections in the series is therefore sucessively lower. ‘Therefore, there isa diretion of descending temperature of steam supply from the frst erytallzation section tothe lst ‘exytallization setion inthe series 10034] Purge of ammonium sulfate solution acording to the present invention is typically to the next crystallization section inthe series. This is wit the exception that the purge from the final crystallization section is discharged rom the 10035] _Asused herein, the term substantially equal produe- ‘ion espacty’of ammonium slate erysas mans that peo- ‘duction capacity typically deviates hy les than 10% between ‘estalliztion sections, Preferably, iti less thon 5%; more preferably less than 2%, Production capacity is typically mea- $e s mass of pret produced in wit time. For example, inky per hour, or kilotons per annum (kt) {0036} Concentration factor isthe rato between te ig streams entering the crystallization sevtion and the liguid streams leaving the enjstallization section. Concentration factor is defined as mass of solution of ammonium sulfate ‘entering the entalization wnivmass of softion of ammo- nium slate exiting the erysalization section. For example incase the feed of tesh solution of ammonium sulfate enter ing erysallization section equals xky/s;the feed of solution ‘of ammonium sulfate purged from another erystaliztion section and entering erysalization section equals y kes nd the purge of solution of ammonium sulfate exiting ens. tallizaton section A equals to 7 kw, then concentration fae- tor becomes (x+y) 10037] Typically, the erystalization sections are heat inte- rated by means of steam, Steam is eal available as het source on chemical production faites Jul. 28, 2016 [0038] Typically, freetion of said solution of ammoniu sulfates purged fom eacicrystallization section in the serie to the next crystallization unit in the series, as defined by descending temperature of sears supply, wi the exception thatthe purge from the final crystallization section in the series is dischanged from the series. In such a way impurity build-up in each of the erystalization sections is avoided, except for i the final erystallization section in the series Typically, n each ofthe crystallization sections the concen {cation of impurities will be lower than thenon-purze coupled prior ar system, except for the final erystalization section, ‘where impurities will be concentrated. [0039] system whercin ammonium sulfate solution is purge to the next erystallization section inthe series means ‘hat impurities are concentrated in the last erystallization section in the series. Accordingly the produced erystals ean be further processed asa particulary pre prot anda less pure product. Or the produets can be combined to produce & radtct which son average more pure han a system without purge coupling, [0040] For any given series of crystallization sections, itis prefer thatthe crystallization sections are each ofthe same Size and type, because of lower investment costs. Typically, cach crystallization section has substantially equal produc- ‘ion capacity of ammonium sulfite erystals. The production ‘capacity is important, because the steam used from one effect {is wsed for the nex! effec, as described in Kristjansson in Geothermies 21 (1992) 765-771. [041] A further advantage of having substantially equal production capacity is that equipment can be standardize. Te erystallizer and the separation units for example cent {ges and filters, are preferably respectively each ofthe same ‘ype. [0042] In principle, any numberof erystallization sections ‘ay be used in the series. However, typically, the series comprises from two to four crystallization sections. Typ cally, each crystallization section comprises an Oslosiype tnysalizer. Oslo-ype crystallizes are particularly stable Torte present invention because they are capable of prodne- ingerystals of anger mean median diameter. That isin eneral ‘desirable for ammonium sulfate crystals [043] The operating temperature ofthe fisterysalization section is determined by the temperature of the available ‘Steam, The temperature othe last crystallization section isin zener determined by the temperature of the available cool- ing medium, The total numberof crystallization sections is determined by the temperature diference between the frst and Last section, as ceseribed by Kristjansson in Geothermies 21 (1992) 768-771 [0044] Accordingly, typically, the temperature of steam entering the frst crystallization seeton inthe series is from 80° C. to 160°C. Preferably itis from 100°C. w 140°C, for example 120°C. [0045] Typically, he temperature of steam exiting the lst exystalization section in the series is from 40° C. to 60° C. Preferably, itis from 45°C. 10 55°C, for example 50° C. [0046] Typically, the production capacity of ammonium sulfate erysals of each erysalizaton section ison the seale of thousands of tons per year (kilotons per annum; kt). Preferably: iis from 10 ka to 200 kia. More preferably, the production capacity ofeach crystallization section is fom 30 Kato 150 kt [047] As mentioned shove, crystals ofa larger size are preferred, because they generally have a layer evomUS 2016/0214868 AI value. Typically, the mean median diameter of crystals pro- ‘duced is greater than 0 mm. Preferably, the mean mesa ‘diameter of the ammonium sulfate erytals discharged is Irom 10mm to 4.0 ma, [0048] The solution of ammonium sulfate is typically an ‘aqueous solution. It may also contain impurities. Typical impurities arise fom the method by which the salution of ‘ammonium sulfate is produced. Preferably, the solution of ‘ammonium sulfate i produced from s process for producing ‘caprolactam or aerylonitrile. Accordingly, the impurities, present are typically those commonly produced in such reae- tions and/or already available in its raw materials [0049] Thetemperature drop of steam applied to each erys- talization section is determined by the Boiling point of the solution of ammmoaiuin sulfate in each erystllization section. AA further, unexpected elect ofthe present invention shat the lower impurity concentration causes the boiling poiat of the solution of ammonium sulfate to drop. Accordingly ess heat needs to be transferred to the erysalization section to evapo- rates given amount of solvent. nother words, ess energy. for ‘example steam, is required to produce a certain volume of ‘epstls. Or, steam of a lower inp temperature may he wi lize. 10050] In the apparatus ofthe prevent invention, typically, ‘each crystallization section isconmectedby a purge line othe next crystallization section in the sores, as defined hy descending temperature of steam supply. with the exception that the purge from the final erytallization section is cise ‘charged from the series. 0051} Typically, each crystallization section comprises an ‘evaporative erystallizer and soli-liquid separation equin= rent. The erystallizer may be of any suitable type, However, preferably, each crystallizer is an Oslo-ype crystallizer Solid-lighid separation equipment means any equipment sit- able to separate ammonium sullate erystas from a solution ‘comprising ammonium sulfate, It may include a continuous ‘ter «centrifuge, a decanter, an elutration column. salt leg ‘ora combination thereof. For example, it may comprise asa, Jeg in combination with an eluration column and a eentr- {ige. Typically, ater leaving the crystallization section the resulting ammonium sulfite crystals are discharged toa dry- ing section. Crystals from each crystallization section may be ‘combined either before or after drying. [0082] The apparatus of the present invention is typically ‘an ammonium sulfate erystallizstion plant. Typically, sueh a plants integrated with another chemical plant. For example ‘a plant of the production of caprolactam or eyelohexanone ‘oxime. Capacity of the ammonium sulfate erystallization plants typically selected based on the volume of ammonivm ‘ulfte solution dischanged from another chemical plant, Fur- ther, crystallization section size i selected based on optimom ‘conditions. Typically, the production capacity of ammonium, sulfate erystalsof each erystallization section is from 30 kato 150 ka, 10053] "The presen invention will be more Fully exphined With reference to the following drawings. [0054] FIG. 1 describes an embodiment ofthe prior at, ‘wherein four erystallzation sections are arranged in parallel in view of the feed of solution of ammonium sulfite, FIG, 2 deseribes an embodiment of the present invention, wherein the pune lines are adapted to discharge a fraction of solution ‘of ammonium sulfate from the erystallization sections. [W055] FIG. 1 describes an embodiment ofthe prior at. Four crystallization sections (1), (2), (8), (4), each compris- Jul. 28, 2016 og a erystallizr of equal size are arranged in parallel with respect othe feed of ammonium sulfate solution. A solution ‘of ammonium sulfate passes through feed line (8) into each tenystallization section, where crystallization occur to orm a slury of ammonium sulfate erysals in an ammonium sulfate solution. Steam is fed to the crystallization section (1), via Tine 6), where itis used to evaporate solvent from the ammo- nium sulfate solution, thereby siding crystallization, The steam does not direely coniet the ammonium sulfate solu- tion, but transfers heat indirectly thereto via a heat exchange ‘unit A solvent-comprising vapor seam is formed in erystal- lization section (1), and is discharged through line (7) t0 crystallization section (2), where it used to evaporate sol- vent, analogous to the process in crystallization section (1). The solvent-comprising vapor stream formed in erystalliza- tion section (2) s discharged through line (8) to erystalliza- ‘ion Section (8) whee itis used to evaporate solvent anal 200s to the process in erystllization section (1), The solven ‘comprising vapor stream formodin crystallization section 3) is dischanged throwgh line (9) to crystallization section (4) ‘where's used to evaporate solvent analogous tothe process in erystallization section (1). The solvent-comprising vapor stream formed in erystallization section (4) is discharged Via Jine (10)- Ammonium sulfate crystals are discharged from enystalizaton section (1) though line (11) for further pro- ‘essing. fraction of ammonium sulfate solution comprising ‘impurities is purged through fine (12). Ammonium sulfate cenjstals are discharged from exysallization section Q) ‘though line (13) fr further processing. fraction of solution fof ammonium sulfate comprising impurities is purged ‘through fine (14). Ammonium sulfate crystals are discharged {rom crystallization section (3) though line (18) for furer processing. fraction of solution of ammonium sulfate com- prising impurities is purged through line (16). Ammoniuz Sulfate crystals re discharge from crystallization section 4) ‘though line (17) fr further processing. fraction of solution fof ammonium sulfate comprising. impunties is purged ‘through fine (18). Optionally the ammonium sulfate crystals from lives (11), (13), (15) and (17) are combined, either before or after any further processing step. The solutions of ammonium sulfate purged through lines (12), (14), (16) and (8) ace treated as waste, and undergo further processing. (Optionally, these solutions of ammonium sulfate sre com bined [056] FIG. 2 describes an embodiment of the present Savention. The system is essentially the sameas that of FIG. 1 Specifically, erytallization section (I) the feed of solution of ammonium sulfate (5); the steam system (6). (7) (8) (9) (10; the four ines through which ammonium sulfate crystals fare discharged from the erysallization sections (11), (13), (13), (F7);and purge fine (18) are identical to those of PIG. 1 ‘The purge lines (12). (14) and (16), ae adapted to discharge 4 fraction ofthe solution of ammonium slate fom erystal- lization sections (1), 2) and (3), respectively to erystaliza- ‘ion sections (2), 3) and (4), respectively. Crystallization sections (2), (3) and (4) are adapted to receive a purge of solution of ammonium sulfate. Accordingly, faction ofthe solution of ammonium sulfite purged from crystallization soction (1) via fine (12) into crystallization section (2); a faction of the soltian of ammonium sulfate is purged from enystallizaton section (2) via fine (14) into crystallization section (3); and a fraction ofthe solution of ammonium sul- {ites pang from crystallization section (3) va ine (16) into exystallization setion (4).US 2016/0214868 AI 10057], Theiavention s illustrated by but not intended to be Timited wo the following Examples. [0058] The Examples are based on a simple calculation using approximate parameters. Input parimeters are repre- sentative operating ammonium sulfate crystallization plant data, These parameters are the total production eapaciy ofthe system, the target yield of the rysalization, and the separa- tion factor (a feature ofthe crystal system). The separation factor and the total production rate of ammonium sulfate ‘egstls are cach respectively equal for eae of the following ‘examples, as discussed in detail below. In the examples al, fresh feeds and all purge streams of solutions of ammonium sult, ineloding any impurities, do not contain solids, (COMPARATIVE EXAMPLE 10059] In this comparative example a parallel ammoni sulfate erytalliztion system substantially as described FIG. 1is used. An aqueous ammonium suliate lye contining ‘on dy base 0.05 wt, % of impurities (—(weight of impurities, in ye)((weight of impurities in lye)+(weight of pure ammo- nium sulfate in lye) is erystllized by evaporative erystlli- zation in a set of four erstallization sections of equal capac- ity, arranged inseries. The total produetion rate of ammonium silat erytalsis 100kta (on dry base: so, impurities and pare ‘ammonium sulfite). Accordingly, 25 kta of ammonium sul fate enystals are produced per crystallization section. The ‘otal purge comprising steams (12) (14), (16) and (18) is 2 kta (ondry basis:s0, impurities an pure ammonium sulfate) “This implies that the total fesh fod comprising steam (8) is 102 kia (on dry base: s0, impurtics and pure ammonium sulle) 10060] ‘Thus, the otalyield of ammonium sulfate crystals is about 98 0wt % (100 kia ammonium sulfate crystals divided by 102 kta fresh food. 10061] Therefore, the feed per crystallization section is on ‘dy base 25.5 kta (pure ammonium sulfate and impurities) ‘anu the purge pererstallization section is on dry base 0 Skis (pure ammonium solfate and impurities). The concentration ‘tor ofthe impurities in each enystallzation section is SL (25.5 kta fresh feed divided by 0 kta purge), and the con- ‘centration of impurities in the purge steam of each crystal- lization section ison dry base about 2.4 wi. % and hence the ammonium sulfate erystalsin the streams (1), (13), (18) and (17) contain about 0.0024 wr. % impuitis. Example 1 [0062] _In Example 1 a coupled sluny system substantially as described inF1G,2is used, The total fresh feed comprising stream (8) is 102 kta (on dry base: so, impuritos and pore ‘ammonium sulfite), the total production rate of ammonium, sulle crystals in the streams (11), (13), (15) and (17) is 100 kta (on dy base: so, impurities and pure ammonium sulfate) ind the total purge, stream (18) is 2 kta (on cry base: s0, impurities and pure amavonium sulfate). The system is oper sted substantially as deseribed forthe Comparative Fxample, ‘except that the amount of purge from one erystallization section o the next i controlled, as are the fresh feed ates to ‘each crystallization section (described in Table 1, below), Here, in contrast to the Comparative Example, the feed rates {or the diferent crystallization sections are nt equa Jul. 28, 2016 TABLE 1 Fearn = Fi Impure ntess Sos Rctmprsow 0 Sotelo revue Tpurpinoited Sas fe Ect 4s as ‘nur a 3 tale cae 8) [0063] Total feed is defined us sum of fresh feed and purge {rom previous eystallizston section, [0064] The third crystallization seeton is taken here as an ‘example, the rests forthe other enstalization sections ean be oblsined in similar manner. Ia the third crystallization section fresh feed comprising on dry base 32 kta (99.95 wt. % Ammonium sulfate and 0.03 wt. % impurities) anda purge fom the second erystallization section comprising on dry base 14 kta about 99.77 wt. % ammonium sulfate and about (0.23 wt % impurities) enter. The total amount of impurity charged to the thind crystallize is about (32 Kta times 0.05 ‘WU%6414 ka times 0.23 wt. %)0.048 kt, The mean impurity ‘concentration ofthe total feed is on dey base (32 kia times 0.05 wi. 14 he times 0.23 wt. 99/82 Ktae 14 ia)) 0.104 ‘wt %, The purge from the thin crystallization section com- prises dry base 21 ka (ammonium sulfate and impurities). Te concentration factors total feed being sum of fresh feed and purge from second erystallization section divided by purge o third erystallization section; so, 46 kta divided by 21 Kia) about 2.2, The total production rate of the third erystal- Jization section is 25 kta ammonium sulfate erystas (on dry base: so, impurities and pure ammonium sulle). [0065] The concentrations of impurities in the purge from the thin crystallization and inthe produced ammonium su- {ate erystals are simply obtained from the folowing mass balance equation: ng prem ing sy ig where [0066] imp*total amount of impurity charged to the ‘hind exystallizer (kta) [0067] purge*"-purge on dry base of third erystallizer (ka) [0068] imp*""*impurity concentration in purge of thin! erysalizer (wt, %) [0069] crystal®—prochicton of ammonium sulfate erys- {alsin third crystallize (kta)US 2016/0214868 AI which (Gimp! yaeparaion Beto) is Gan" =™ 1000 {0071} After substiuton i flows tat the iampity cone ‘entation in pure of tied exytalization section is on ery ‘weit ase about 0.23 Wt 9%) 10072} The separation fet 100, s0 the concentration ‘of impurities i the ammonim sulfite crystals proce 3 the third crystallization section is (023 wi. 50/1000) is (0.00023 wr. 10073] _As can be soon fom the above ress the wt. % Soopurties in the ammonium sulfate crystals prodiced ia exytlization sections (1), (2) and @) of Example 1 are Ssbatntlly ker thao fr the smmonin sollte crystals prodiwed i erystallzation sections (1), (2) and (3) ofthe Comparative Example (0.00023 wt. 98-0 0024 wi). The 1% impurity of ammonium slate crystals produced in ‘xstlizationseton (4 of Example 1 only fe percent higher than the wt % impurity of ammonium slitecrystals produced in enstallization ston (4) of the Comparative Example (00025 wr. % vs. 0.0028 wt. %) {0074} Further. ifthe ammonium sulfate erystals produced ‘ncrystalization sections (1), 2) @)and(4) in ample ee mixed, the mean wt. impure ofthe combined smimo- nin sulfate ery 6 then about 0.0008 wt. %e which is fubstntilly lower than the scan wt. 8% impurities ofthe combined ammonium sulfate exstas in the Comparative Example (beng 0.0024 w.%) 10075] Comparison ofthe results of Example 1 with tose ‘of the Comparative Example clearly shows that the page system of the resent invention reduces mean impunity con- teat inthe crystalline atunoniun sult prodoced, while the toa yieldof ammonium slate crystals remain uachanged. Example 2 10076] _In Example 2 « coupled slury system substantially as described in FIG. 2 was used, The total production rate of ammonium sulfate erystals inthe steams (11), (13), (18) and, (17) is 100 kta (on dry base: so, impurities and pure ammo- nium sulfite. The mean impurity content of ammonium sul- {ite crystals produced in crystallization sections (1), (2) (3) ‘and (4) is about 0.0024 wt %, which is equal to the mean Jmpurity conten of ammonium sulfate erystals produced ia ‘en’tallization sections (1), 2), (@)and (4 inthe Comparative Example. The system is opersted substantially as desribed for the Comparative Example, except that the amount of png from one erystallization section to the next was con- teoled, as were the fresh feod rates to each exystallization section (described in Table 2, below). Here, in contrast to the ‘Comparative Example, the feed rates forthe different crys talization sections dre no equal, 10077] The obtained results are given in Table 2. TABLE 2 staan 1 a4 Inouye et tos “Os “hss Jul. 28, 2016 TABLE 2-comtinved Comiion ‘aw dom prviow os ss ‘ylation stn a) Apri ge Oe cot one oa) Som pees atalino ston purity nto fed ‘o0s 0.089.089 0.16 Pave toon os Input pe on dae 3 ‘mali sts tale cae 8) [0078] Total feed ie defined as sum of fresh feed and purge rom previous erystallzaton section 0079} As can be seen from the above results, the wt. % impurities in the ammonium sulfate crystals produced in enysalizaton sections (1), (2) and (8) of Example 2 are substantially lower than for the wmonium sulfate crystals produced in crystallization seetions (1), (2) and (8) of the ‘Comparative Example (0.00020 wt. % v8.0.0024 wt. %). The ‘wt % impurity of ammoninm sulfate crystals produced in crystallization section (4) ofthe Example 2s higher than the ‘Wi. % impurity of ammonium sultate crystals produced in enystallization section (4) of the Comparative Example (0.0091 wi. % vs, 0.0024 wi, %). The mean wt. % impurities ‘ofthe combined ammonium sulfate erystals produced inerys- ‘alization sections (1), (2), (3) and (4) in Example 2 is about 0.0024 Wt. [0080] In Example? thepurgeoferystllizaton section (4) js ust 0.52 kta (on dy base: so, impurities and pure ammie- itm sulfate). This means that the total fresh feed oa dry’ base to all crystallization sections is (sum of total amount of ‘ammonium sulfateerystals produced ondry base and purgeot ‘enysalization section (4.0m dry base) just 100.52 kta. So, the {otal yield ofammonium sulle crystals iss high as (100 kta divided by 100.52 kta) 99.5 wt. %. [0081] | Comparison of the results of Example 2 with those fof the Comparative Example clearly shows thatthe purge system of the present invention increases the total yield of ammonium sulfate crystals, while the mean impurity content a the produced ammonium sulfate crystals remai ‘unchanged, 1. continous process for producing ammonium sulfate crystals, wherein said process comprises 1) feeding to a series of erysalization sections, which crystallization sections are het integrated in series, Solution of aramonium sulfate: ii) crystallizing ammonium sulfate crystals fom said solu tion of ammonium sulfate; ill) purging a faction ofthe solution of ammonium sulfate fom each of said crystallization sections; and jv) discharging smmonium sulfate crystals fom cach ery tallizaton section, characterized in thatUS 2016/0214868 AI «fraction of said solution of ammonium sulfate is pursed from at least one erystllization soction to at least one other erystallization section, 2.A process according o claim 1, wherein the erystlliza- tion sections are heat integrated by means of steam, 3.A process according to claim 2, whereina friction oid solution of ammonium sulfite is purged from each cystll- ation section inthe series tothe next erystallization unit in the series, as defined by descending temperature of steam supply, with the exception thatthe purge from the final crys- talization setion inthe series is dischargod from the eres. 4. A process according to claim 1, wherein each erystali- zation section has substantially equal production capacity of ‘anumosiun sulfate erytals '5. A process aeconding to claim 1, wherein the series com= prises from two to four, crystallization sections. 6.A process according to claim I, wherein each crystalli= zation section comprises an Oslo-type crystallizes 77.4 process aconing to claim I, wherein the temperature ‘of scam entering he first crystallization setion inthe series is from 80° C- 10 160° C. 8. process aocordig to claim 1, wherein the temperature ‘of steam exiting the last rystallizaton setion inthe series is rom 40° C, to 60? C. 9. A process according to claim 1, wherein the production ‘capacity ofammonium sulfate crystals ofeach erystaliztion section is from 30 kta 0 150 kta 10, A process aecording to claim 1, wherein the mean median diameter of the ammonium sulfate crystals dis- ‘charged is from 1.0 mm 40 mm. Jul. 28, 2016 11. process according to claim 1, wherein the solution of ammonium sulfate is produced froma process for producing ‘caprolactam or acrylonitile, 12, Apparatus suitable for producing ammonium sulfate cenystals, comprising {a series oferystallization sections of substantially equal Production capacity of ammonium sulfate erystals, ‘which are configured tobe heat integrated with respect to steam: ii) a steam supply system integrating the crystallization sections in series; il) food of ammonium sulfate solution; and ivjasystem of removal ammonium sulfate crystals; char ‘clerized in that, at least one erystallization section is connected by a purge line to another exystalization setioa inthe series 13. Apparatus according to claim 12, wherein each onys- tallization section is connected by a purge line to the next crystallization section inthe series, as defined by descending ‘temperature of steam supply, with te exception that the purge ‘rom the final erystallizaton section i discharged from the 14, Apparatus acconting to claim 12, wherein each enys- tallizaion scction comprises an ewsporative erystalizer and sol-tquid separation equipment. 18. Apparatus according to claim 12, wherein the progue- sion capacity of ammonium sulfite crystals ofeach crystal ‘ation seoton is from 30 kt to 150 kts.