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    US 20151 cu») United States 4726681 cz) Patent Application Publication co) Pub. No.: US 2015/0147266 Al Mollerhoj ($4) PROCESS FOR THE OXIDATION OF S02 TO 803 Applicant: Haldor Topsoe A/S, Kas. Lyngby (DK) Inventor Martin Mollerho}, Bitkerod (DK) AIS, Kas. Lynaby (DK) Assignee: Haldor Topso (21) Appl. No: 14/406,188 (22) PCT Filed: Jun, 3,2013 (85) PCTNo: — PCTIBP2oL:/N61342 $371 M0, ()Date: "Dee, 2014 G0) Foreign Application Priority Data Jun. 6.2012 (EP) PCTIRP20120060703 Publication Classification () Ince corB 1780 (2005.01) OLB 176 (2005.01) BOL 82 (2006.01), (43) Pub, Date May 28, 2015 (52) US. coc \COLB 17/806 (2013.01): BOLI #70285 (2013.01): CO1B 17776 2013.01); BOIS 2208027 (2013.01); BOL 220800256 (201301), on ABSTRACT ‘The present invention relates toa process plat forthe oxida tion 6f SO, to SO, in a process gi, said process plant com- prising a feat exchanger configured for heating the process {as by heat exchange with an oxidized process gas andor @ Turther oxidized process was by providing thermal contact between sid process gas and said oxidized process gas and/or sid further oxidized process gas, a frst zone of material catalytically active in oxidation of SO, to SO,, and a boiler ‘configured for containing steam being heated by the oxidized process gas andor the furher oxidized process after said ‘oxidized process gas has been cooled in the heat exchanger characterized in the cooled oxidized process as in the boiler being non-condensing with the benefit of providing the pos sibility fora smaller heat exchanger which may be made With ‘only moderate corrosion resistant materials, compared to 9 process plant according to the prior at as wel a a related process Patent Application Publication May 28,2015 Sheet 1 of 10 US 2015/0147266 A1 Fig.1 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 0% Patent Application Publication May 28,2015 Sheet 20f10 US 2015/0147266 Al Patent Application Publication May 28,2015 Sheet 3 of 10 US 2015/0147266 Al Patent Application Publication May 28,2015 Sheet 4 of 10 US 2015/0147266 Al Patent Application Publication May 28,2015 Sheet Sof 10 US 2015/0147266 Al Patent Application Publication May 28,2015 Sheet 6 of 10 US 2015/0147266 Al Fig.6 Patent Application Publication May 28,2015 Sheet 70f 10 US 2015/0147266 Al Fig.7 Luyewn] 8 8 8 8 ° ----Ll 7 | | © TTS] ole ee 7 I eo a | joo ~ | ae oe Patent Application Publication May 28,2015 Sheet 8 of 10 US 2015/0147266 Al Fig.8 10 5 [he] 320 310 300 9 280 270 260 [90] Patent Application Publication May 28,2015 Sheet 9 of 10 US 2015/0147266 Al Fig.9 10 5 [hr] 320 310 300 20 4 280 270 260 f9.) Patent Application Publication May 28,2015 Sheet 10 of 10 US 2015/0147266 Al Fig.10 -7 2 cae \ -7 ° \ _- / © 2 Caace = . ) _- «lt © ~e N oe ced of 7S -"- « ) 2 ¢ “4 ° \ ) ¢ a \ \ \ S N N s _? se2eesgee2e2seeeee8 8¢ss 28888 8 8 38 8 8 &5 8 ® &€& R 8 US 2015/0147266 AI PROCESS FOR THE OXIDATION OF S02 TO ‘sox [0001] Sulfuric acid, H,SO,, is made by oxidation of SO, ‘na feed gas to SO, and subsequent hydration to H_SO,.The SO, feed gas can come from various sources. One type is ofT ‘gases from smelters and roasters, Such feed gases are sup= plied cold and water saturated, typically at 20-80° C., and they contain from about 0 [Yeval. SO; toabout 20% vol, SO,, In onder for the SO, to SO, conversion eaetion to run at & reasonable rate, the cold SO, containing feed gas has to be hated! to about 400° C, befdee iis directed o the catalytic bed. 10002] | While the feed gas may be partly heated by eg. hot ‘cooling ar from a wet gas Sulfuric Acid condenser the final heating to about 400° C. is typically done using the reaction heat from the SO, converter, as this is the only place in the unit, where sueh high temperatures are available. In particu- high temperature otlet from the 1 catalytic bed is advantageous as temperatures well above 400° C. are Fexjired vo heat the feed to 400°C. [0003] | When the SO, content in the process gas slow (e.g. Jess than about 2.5% vol, the eaction heat is insulicent t0 heat the fas! gas. Energy’ will have to be ake, typically by director indirect support-firing, encurring a further cost of vel, To. minimize the periods where supportfiing. is required, the thermal control of a sulfur acid production plant is important bu the exiifty of thermal management Js limited by a number of eonsiruints. For oxidation of SO, 10 0, to be sufficiently fast, the reaction most take place at & temperature of at least 370.400° C. Atthe same time the SO, ‘containing oxidized product gas must be cooled to shift the product equilibrium towards SO,, which limits the tempers- ture anc finally gas temperatures must he kept above the dew point of sulfuric acid, since condeased H,SO, isin general very cortosive while H,S0, in the gss phase is almost not ‘corrosive, Fialy the hydration reaction for SO, is exother- mal, which reduces the temperature approach in heat ‘exchangers for wet sulfurie acid gases below about 400° C. 0004) Traditionally the thermal management ofa sulfuric ‘acid plant for processing a raw process gas has involved ether ‘gtsigas heat exchange, or heat exchange facilitated by an appropriate heat transfer medium such as molten salt Steam, has not been a relevant heat transfer medium, since the pro- ‘cess gas temperature obtained hha been insufficient for providing the sulicent temperature {or SO, oxidation [0005] German patent application DE 195 22.927 Al pro- Vides a method for production of concentrated sulfuric acid 80, and partial condensation of sulfuric acid in boiler. in ‘which the H,OISO, ratio is limited t0 the range 0:9-1.1 Sulfuric acid is hydrated and condensed in © boiler with @ ‘team pressure around 20 bar, wih hea exchange tubes made from steel, Fora narrow range of sulfuric acid concentration, the liquid sulfuric acid is only moderately comosive, and regula stainless see! may in theory be an acceptable mate- Fal. However, if the stiet control of H,O/SO,, is not adhered to condensed sulfuric acid may eause corrosion and leakage ‘0f20 bar steam ito sulfuric aid condenser, which may be critical [0006] | Now aecorting to the present disclosure i has been ‘ound that by ensuring thatthe cooled oxidized process pas is non-condensing’ in combination with combined heat ‘exchange, ie, by using a boiler producing steam for heat May 28, 2015 cexeliange in combination with ether gas/aas heat exchange, for heat exchange facilitated by eg. a molten salt as heat transfer medium, the temperature approach of the heat exchanger can be increased significantly, resuling in a reduced heat exchange area, and thus significant savings in cost, Furthermore by ensuring that the temperatures are sch that the cooled oxidized process gas is non-condensing the HOVSO, ratio is not eritical and the heat exchanger materials 446 not have to be able to withstand the corrsiveness of condensed sulfuric acid. The cooled, but non-condensing. ‘oxidized process gas may'be transferred w a downstream air cooled condenses, n which sulfuric acid is condensed, and in ‘which the cooling medium ishavinga pressure close to thatoF the cooled oxidized process gas. [0007] As used herein the tem temperature approach shall be understood as the difference between the cold and the ‘warm stream of a heat exchanger. [0008] As used herein the term heat exchanger shall be ‘understood a process unit in which heat is transferred between a cold stream and a warm sie, in whic the wo streams are physically separated. This means that heat trans- Ter medium facilitated heat exchange typically requires two heat exchangers, Feat exehangers coring to the present invention may be of any configuration, including planar oF tubular, and iay optionally beconfigured with cooting fins.as known tothe skilled person [0009] As used herein gas'gas heat exchange shall be con- struedas hea exchange between cold and a warm steam, ia ‘whieh the thermal contact between the eold and the warm steam only roguires transfer of energy serosa heat exchanger wall [0010] As usod herein the term heat transfer medium f {ated heat exchange shall be consirued as heat exchange between a cold and a warm stream, in which the thermal ccniaet between the cold and the Warn stream requires the ‘movement of a best transfer mesium, [0011] As used herein heat transfer shall mean any process transferring energy from one location to another, including sgas/gas heat exchange and heat transfer medium feelitated beat exchange as described above, but also convection, eon- duction, and radiation which may be involved in the heat transfer from eg. catalytically active material through cool- ing tubes to a process gas or a heat transfer medium. [012] As used hereia the term heat exchange shall be ‘understood t caver any typeof heat transfer including both sgas/gas heat exchange, and heat transfer medium feelitated heat exchange as defined above, [0013] Asusedthereinthe term boiler shall he understood as ‘process unit in which heat i transferred rom a hot process steam to liquid water at its boiling point, such that steam is released, [0014] As used herein the tems eatalyst zone, bed of exta- Jytically active material and catalytic bed stall be consied as equivalent. 0015} As used herein the dew point temperature for ‘component of gas isthe temperate at which the compo- ‘ent condenses from the gas mixture, The dew point is depen- dent on the—pressure and composition ofthe gs mixture ‘The term above the dew point shall be understood os a tem- perature where the as mixture is non-condensing, and simi Tar low the dew point shall be understood as a temperate ‘where the was mixture is condensing. US 2015/0147266 AI 10016] Equipment having minor surface areas having cold spots potentially inducing condensation shall not be con- sirued as condensing gas conditions [0017] As used herein autothermal operation shall be lunderstood to miean operation at a SO, level at which a sue {ure acid plant may operate in steady state with limited or no heat supply, hasedon the reaction hestof the oxidation of SO wo SO, as well asthe reaction heat of hydration of SO, 10 H,SO, and finally condensation of gascous H,8O, to farm Tiguid #80, [0018] ”Asused herein the term thermal circuit shall be used to describe the process from a themmal perspective, substan- tally disregarding the chemical rections and focussing oa the heat transfer related to the process. 10019] | No» shallmoan Normal cubic meter. theamount ‘of gis corresponding to one m” at standard conditions, 0° C, and I atm, 10020] | Where concentrations are stated in % this shall be understood as volumetric %, Unless slated otherwise, the ‘concentrations of SO, and H,O are presented as nominal ‘concentrations, ie, under the assumption of no hydration of $0, 10 H.S0. [0021] | Where the terms partially oxidized process ps, oxi ized process gas and furher oxidized process as are used these tem shall be construed only a specifying process gas in relative positions ofthe same process and not as an indie ‘ations ofthe extent of oxidation across different processes 10022] Ina broad embodiment the present invention relates oaprocess for conversion of SO, to SO, ina rns process as ‘comprising the steps of 10023] _)heating the raw process asby heat exchange with sn oxidized process gas, providing a heated process gas 0024) b) contacting theheated process gas witha first zone ‘of material catalytically active in oxidation of SO, to $04, providing an oxidized process gas 10025) ) withdrawing heat of reaction rom one or both of the fst zone of catalytically setive material and the oxidized process gas tothe raw process gts by one ormoreheat transfer processes taken Irom the group consisting of eonvection, ‘conduction, radiation, gas/gas heat exchange or by heat trans fer medium facilitated heat exchange 10026] 4) further cooling the oxidized process yas by heat ‘exchange in boiler, preferably a water tbe boiler receiving fed of water, providing saturated steam and a cooled ox «ized process gas, in which the raw process gas, the heated process as, the oxidized process was an the cooled oxidized process gas are non-condensing with respect sulfuric acid, ‘withthe associated benefit of efficient thermal management ‘of the process, with reduced heat exchange arca dic to ‘increased temperature approach in the heat exchangers, i ‘comparison with the thermal management of the process Jayout aecording to the peior at, while atthe same time the process equipment may’ be made from moderately priced ‘materials as corrosion resistance isnot critical, and furher- ‘more the temperate variation ofthe cooled process gas Will be low, providing simpler operation of equipment down- 10027] In a further embodiment the process further com- prises the steps of contacting the heated process gas with one ‘OF more furhee zones of material catalytically ative in oxi dation of SO, to SOs, providing a further oxidized process as, cooling the oxidized process gas andor the further oxi- ddized process gne by heat exchange with the a process gs upstream the fist one of catalytically ative material, in one May 28, 2015 ‘or more heat exchangers, configured either as inter-bed cool- rs, as heat exchangers extemal to the reactor or as integrated hat exchangers in contact wit catalyst, with the associated ‘benefit om the use of multiple catalyst zones of providing more optimal temperatures for the oxidation reaetion and for the oxidation equilibrium, [0028] In a further embodiment the process further com- Drives the step of pre-heating the raw process gas by heat exchange with a steam How, preferably condensing steam, prior to heating the process gas by heat exchange with the oxidized process gas, providing a pre-heated process gas, ‘with the associated benefit of employing the energy available inthe team to ensure non-condensing and thus non-corrosive conditions in the downstream heat exchanger, by ensuring that the temperature ofthe cok raw process gas side of the heat exchanger is above the dew point of H,SO, in the warm oxidized process gas. Furthermore this pre-hesting ensures that energy remains in the process such that auto-thermal ‘operation is possible with lower concentrations of SO,, [0029] In a further embodiment the process further com- prises the step of mixing aprocess gas upstream the frst zone ‘of catalytically active material with arevyeled warm process ‘28, wih the associated benefit of employing the heat sv able in the reeyeled process gas fo ensure non-condensing ‘onions in the downstream heat exchanger [0030] Ina furiber embodiment the beat exchange beween the raw process gas and one or more of the oxidized process gs or the further oxidized process gas isin part made by ‘gas/gas heat exchange, wit the associated benefit ofa simple beat exchange cireuit, [0031] In. furiher embodiment the heat exchange between the raw process gas and one or more of the oxidized process gs, or the further oxidized process gas is made in partby heat exchange facilitated by a heat transfer medium, such as mol- ten salt, withthe associated benefit ofa heat exchange cir witha possiblity for beat storage in a buller of heat transfer ‘medium. The heat transfer medium may comprise molten salts such as an eutectic mixture of sodium and potassinm tate andr nite oF an cil. I is prefered that the heat ‘eunsfer medium las «boiling point above 480° C. [0032] Ina further embodiment te ra process gs luctu- fates in one or more ofthe parameters flow rate, presstre and ‘SO, concenteation, wit the associated effet of providing a process enabled to clean the Feed gas while safely and ell- ently maintaining the process as temperature atthe inlet to the silfric acid condenser within the allowable limits, between te sulfur acd dew point and the maximum allow able operating temperate, in dependence of downstre materials. {0033} Ia a farther embodiment the temperature of the steam is at east 10°C, preferably 15® C. above the H,SO, dk point ofthe eoted oxidized proces as with the 2350" ciated benefit of providing a temperature ofthe cooled ox ized process gas suficiently high for avoiding omosion problems di to condensation of sulfur seid [034] In a further embodiment the temperature of the stoam is at least 200° C., preferably 240-310° C. and even ‘more preferably 250-280" C., with the asseeiated benefit of providing a eooled oxidized process gashavingatemperatire above the dew point of a process gas containing at least respoctively 0.1% vol, SOs, 0.1-20% vol. SO,, and 0.1-7% vol. SO, US 2015/0147266 AI 10035] In a farther embodiment the raw process gas ins atleast 2% H,O with the sociated benclitof providing water for hydrating SO, for a downstream condensation of sullurie ai 10036] Ina further embodiment the pressure of the steam is 30-100 barg, preferably 40-8Obarg and even more preferably 40-60 arg, with the associated benefit of providing a process ‘with a higher steam temperature due to an increased water boiling point as well as steam eireuit matching the require- ments of high pressure steam turbine 10037] In further embodiment the hested heat transfer medium is cooled by heat exchange with boiling water oF steam with the associated benefit of providing the energy ‘collected from the exothermal oxidation processin accessible orm for the eomainder of the process 10038) _A furtheraspectofthe present disclosurerelatesto 2 process for production of sulfuric aed involving conversiy ‘0f80, to SO, andsubsequent condensation of sulfuric acidin condenser cooled by heat exchange with a gas suel as process gas or air, with the associated benefit of providing @ process in whieh the process heat exchange is separated rom the corrosive condensing conditions, such that process ‘equipment materials upstream the condenser does not haveto be coerosion resistant 10029] A further aspect ofthe present disclosurerelatest08 process plant for the oxidation of SO, to SO, ina process pas, said process plant comprising heat exchanger configured for heating the process gs by heat exehange with an oxidized process gis andor funlter oxidized process pas by provid- ‘ng thermal contact between said process gas and said oxi ‘ized process gas andr sid further oxidized process 25, 3 first zone of material catalytically active in oxidation of SO {0 S0,, and a boiler configured for containing steam being heated bythe oxidized process gas and/or the furher oxidized process after suid oxidized process gas has been cooled in the hat exclunger characterized inthe cooled oxidized process sin the boiler being non-condensing with the benefit of providing the possibilty fora smaller heat exchanger which may be made with only moderate erosion resistant mater- als, compared toa process plant according to the prior art 0040] Ina further embodiment this process plant furher ‘comprises heat transfer mem circuit configred for pro- viding heat transfer medium for facilitated heat exchange in ‘one or more of sad hea exchangers, providing the possibility or heat storage in the heat transfer medium and for voiding pavpas heat exchangers, which are expensive, large and ‘hich may pose control scheme challenges. 10041} Ina typicel process layout scconding to the prior at at steady slate processing, aw process gas is heated in the process gas heater to about 400" C. The hot process 208 is directed fo the eonverter and the SO, is partially oxidized in the 1” catalytic bed generating « temperature increase of about 25°C. for every 1% SO; inthe feed. eg. to about 475° C.for 3% SO,, To ave high conversion inthe converter, it dueto the equilibrium between SO, and SO,,nec-essary (0 ‘eool the process gas before luther conversion can. be ‘achieved, Therefore the process gas is cooled io around 400" C. before the gas is drsctedto the 2” cetalytie bed or further ‘conversion, If even higher conversion is required, a further ‘cooling/sanversion step canbe added. Finally the process gas js cooled in the oxidized process gus cooler toa temperstre hove the dew point temperature of sulfuric acid, typically to temperature between 270-290" C., suc thatthe materials i May 28, 2015 the SO, converter may be chosen without considering the high corrosion resistance required where there is risk for condensation of suliri acid, [0042] For cold aw process gasses (below 200” C.), beat recovery systom with molten saltas energy carriers often the preferred choice, in which, the molten salt is heated 10 ‘medium temperature inthe oxidize process gas cooler and 10 high temperatures ina converter heat exchanger, which may be configured either as an inter-bod cooler (between beds of catalyst), as heat exchangers extemal othe reactor (in whieh process gas stream is withdrawn from the reactor tothe heat ‘exchanger and back to the next bed of catalyst) of as inte- arated heat exchangers in contact with eatalyst (inside the bed ‘featlyst), to oblaina temperature where the ot salt may be used fo heat the raw process gas in the process gas heater. In ‘order to obtain a feed gas temperature of eg. 400° C. atthe inlet tothe converter, thehot sat need to be above 400" C. and preferably above 430° C. In order to eat dhe molten salt 10 8 430° C, the process gas temperature out ofthe I eata- Iytic hed need to he above 430° C., preferably more than 20° above, i. above 450° C. This means that forthe process to ‘un smoothly, the temperature inerease aver the 1” cata bd should preferably he above 60" C. which means that the process gas should preferably contain more than 23% SOs, 0043} A heat recovery system with yas/gas heat exchange fs also known in the price at In this cave the process gas is irectod to be heated to intermestat temperane i the 0 ‘ized process gas cooler and to high temperatures in interbed cooler, such that it may be fed at slieient tempera ture othe frst catalytic hed, While gas/gas heat exchanger saves the cost elated 1 the use of heat transfer medium in @ ‘Separate circ, may also involve praestcal problems a8 it ‘may have to be installed outside the reactor. [044] ‘The thermal benefit of saving the energy transfer 0 And from heat transfer medium may in practice be balanced ‘against poorer gas wall heat transfer coefficients. Therefore inorder to obtain a feed gas temperature of eg. 400° C, inlet the converter the process gas temperature ot of the 1” et Iytie hed need to he abowe 400” C., preferably more than 50° above, above 450° C. This means that forthe process run smoothly, the temperature increase over the 1" catalytic bed should preferably be above 60° C. which means that the process gas should preferably contain more than 24% SO;, [0045] When sulfur trioxide and water are present in the races ga, sulfrc eid wil start to form when the process {288 is cooled below 400° C. in the oxidized process gas cooler, The reaction proceeds aevording to reaction (1) SO,(+8,048)-150¢)241 keaiote o [0046] The hydration reaction is an exothermal reaction, And therefore, lower temperature wll favour the formation of sulfuric acid. This means that the temperature of the process sin the oxidized process gas cooler does not change lin- carly with the amount of energy transfered. Thisean be seen in FIG. 1, which shows heating and cooling curves for the okdized process gs cooler. The sold ne represent the pr ‘cess gas temperatireas a function of the percentage energy ‘eansforred, and the dotashed curve marked by C indicates the corresponding temperature of a molten salt as « heat transfer medium. The process pas cooling curve is conven, ‘cating that thediflernce hetween two lineshasa minima a the heat exchanger, which causes a low overall tem- US 2015/0147266 AI perature approach. Therefore a large heat exchange are is required in the oxidized process gas cooler due to the low ‘overall temperature approach, 10047] _‘Theonly ways to improve the temperature approach with the given process layout are by decreasing the molten salt inlet temperature or by decreasing the molten salt outlet temperature by incresing the molten salt low. The salt ialet temperature is Iimited by he sulfurie acid dew point of the process gas. Thesallemperatureshould always bekep mia ‘mum 10°C. and preferably 15°C. above the sulfurieacid dew point (© avoid sulfuric acid condensation and corrosion. Fur- thermore its desirable to recover as much energy as possible intheoxidized process gas cooler, so normally the molten sll inlet temperature and process. gas outlet temperature is ready a the minimum allowable 10048] _1the salt How is increased, the salt outlet temper ture will decreas, and it may not be possible to obtain a salt ‘temperature atthe inlet ofthe process gas heater whic ishigh ‘enotigh to obtain the required process gas tempernture atthe inet ofthe SO, converter [0049] Furthermore, for feed gases with tuctuationsin flow ‘and SO, concentration, it ean be dificult to contol the te peratures inthe plant. Specifically the process gas tempers- ‘urea the ialet wo the sulfuric acid condenser is important, Oa ‘one hand the gas temperature must be kept above the sulfuric ‘acid dew point ofthe gas to avoid sulfuric aid eondensation land corrosion inthe axcized process gas cooler and ducting between the oxidized process gas cooler and sulfuric acid ‘condenser. On the other hand, the gas temperature must Be kept below the maximum operating temperature ofthe sulf- ricacid condenser, which s typically limited 300°C. dueto the use of uorinated polymers in the sulfure eid eondenser inet. In the process according tothe prior atthe process gas temperature atthe inet to the sufi ace eondenser i yp cally controlled by adjusting the salt flow to the oxidized process gas cooler via feed back PID conte, If this is not fulficent, the eontal ean he ehanged to a combination of feed-forward and feod back contro, where measurements of the feed sow and SO, concentration are ws = input for the feed forward ealeulation ofthe required salt flow, The feedback signal is thea used to correct any measurement ‘error, dynamic effects and other factors which eannot be ‘aeconnted forin the feed forward calculation, However even ‘with combined feed-forvant and feed back contro, it can be

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