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The chemistry of the NONO2–NH3 “fast” SCR reaction over Fe-ZSM5 investigated

Journal of Catalysis256(2008)

312–322

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Journal of Catalysis

https://www.wendangku.net/doc/a010365537.html,/locate/jcat

The chemistry of the NO/NO2–NH3“fast”SCR reaction over Fe-ZSM5investigated by transient reaction analysis

Antonio Grossale a,Isabella Nova a,Enrico Tronconi a,?,Daniel Chatterjee b,Michel Weibel b

a Dipartimento di Energia,Laboratorio di Catalisi e Processi Catalitici,Politecnico di Milano,Piazza Leonardo da Vinci32,I-20133Milano,Italy

b Daimler AG,Abteilung GR/VPE,D-70546Stuttgart,Germany

a r t i c l e i n f o a

b s t r a

c t

Article history:

Received10March2008 Revised22March2008 Accepted27March2008 Available online2May2008

Keywords:

Urea SCR

Fast SCR

Ammonium nitrate

Zeolite catalysts

Diesel exhaust after treatment We present a systematic study of the chemical steps in the NO/NO2–NH3fast SCR reaction2NH3+ NO+NO2→2N2+3H2O over a commercial Fe-ZSM5catalyst.The study is based on transient reaction experiments at realistic conditions for removal of NO x from mobile diesel exhausts.Its goal is to assess and critically evaluate the current ideas on the SCR mechanism,and also to establish to what extent the mechanistic pathways demonstrated for V-based catalysts also apply to Fe-promoted zeolites.Results show that the fast SCR reaction proceeds at low temperature via a global sequence involving NH4NO3or related surface species as intermediates,

2NO2+2NH3→N2+NH4NO3+H2O,

NO+NH4NO3→NO2+N2+2H2O.

Such a sequential scheme is the same as that proposed previously for the fast SCR chemistry over V-based catalysts and other zeolite catalysts and thus is considered a general mechanism.It explains all of the available observations for stoichiometry(e.g.,optimum NO/NO2unit molar ratio),selectivity(e.g., N2O from NH4NO3decomposition),and kinetics(e.g.,rate of fast SCR=rate of nitrate reduction by NO). We further show that the redox reaction between NO and nitrates is the rate-controlling step and is inhibited by ammonia.Remarkably,the same strongly enhanced deNO x activity observed in the fast SCR reaction also was observed in the absence of gaseous NO2but in the presence of surface nitrates.We accordingly propose a general summary of the fast SCR chemistry over V-based and zeolite catalysts that emphasizes the key role of surface nitrates.

1.Introduction

In addition to the well-known“standard”SCR reaction,

2NH3+2NO+1

O2→2N2+3H2O,(1)

the so-called“fast”SCR reaction,

2NH3+NO+NO2→2N2+3H2O,(2) plays a critical role at180–300?C in boosting the denitri?cation (deNO x)activity of new generation urea-SCR converters for diesel vehicles integrated with an upstream preoxidation catalyst that partially oxidizes NO to NO2[1].

Koebel and co-workers[1–4]?rst extensively investigated the fast SCR reaction over V2O5–WO3/TiO2SCR catalysts.To explain the higher rate of the fast SCR reaction,they proposed a redox

*Corresponding author.Fax:+390223993318.

E-mail address:enrico.tronconi@polimi.it(E.Tronconi).mechanism in close analogy with that of the standard SCR re-action,but with NO2serving as a more e?cient oxidizing agent for the vanadium sites than oxygen[3].Furthermore,for the NO–NO2/NH3reacting system,they also reported the occurrence at low temperatures of two side reactions not observed in the presence of NO–NH3only—namely the formation of ammonium nitrate,

2NH3+2NO2→NH4NO3+N2+H2O,(3)

and the decomposition of ammonium nitrate by NO,described ac-cording to the following stoichiometry[4]:

NH4NO3?NH3+HNO3,(4) 2HNO3+NO→3NO2+H2O.(5)

However,reactions(3)–(5)were considered to be side reactions occurring in parallel to fast SCR(1),not participating in its mech-anism[4].

In our work aimed at developing a chemically consistent sim-ulation model of SCR converters for automotive applications[5], we have addressed mechanistic aspects of the fast SCR chemistry

A.Grossale et al./Journal of Catalysis256(2008)312–322313

over commercial vanadium-based catalysts by means of transient reaction analysis[6–10].Our data have shown that the fast SCR chemistry proceeds over V2O5–WO3/TiO2SCR catalysts at low tem-perature via a sequential scheme,which can be summarized as comprising two global reactions—ammonium nitrate formation[re-action(3)]and the following reaction between ammonium nitrate and NO—formally involving NH4NO3as an intermediate:

NH4NO3+NO→NO2+N2+2H2O.(6) In fact,the sum of(3)and(6)yields the stoichiometry of the fast SCR reaction(2).Notably,reactions(3)and(6)are similar to those already reported by Koebel and co-workers,but here they are not just side reactions,but are intimately related to the fast SCR chem-istry.

The mechanism of the?rst step in the fast SCR sequential scheme—ammonium nitrate formation[reaction(3)]—was clari?ed by Koebel’s group[1–4]and implies NO2dimerization(7),dispro-portion(8),and successive reactions between nitrous and nitric acid and NH3(9),(10),with rapid decomposition of ammonium nitrite to nitrogen:

2NO2?N2O4,(7) N2O4+H2O?HONO+HNO3,(8) NH3+HONO?NH+4+NO?2?[NH4NO2]→N2+2H2O,(9) NH3+HNO3?NH+4+NO?3?NH4NO3.(10)

Concerning the second step in the fast SCR sequential scheme—reaction(6)between NO and ammonium nitrate—we have demon-strated by dedicated transient experiments a mechanism based on: ammonium nitrate decomposition(10reverse),successive oxida-tion of NO to NO2by nitric acid,which is thus reduced to nitrous acid(11),and reaction of the latter with NH3to form N2via am-monium nitrite decomposition(9)[6–10]:

NH4NO3?NH3+HNO3,(4)=(10reverse) HNO3+NO?NO2+HONO,(11) NH3+HONO→N2+2H2O.(9) We further observed that the rate-limiting step(6)does not proceed over V-free WO3/TiO2and thus is catalyzed by V2O5.The same results had been previously reported for reaction(5)[4].Ac-cording to a redox interpretation of the fast SCR chemistry over V-based catalysts,the key global reaction(6)actually is associ-ated with a redox cycle involving the more effective reoxidation of reduced V-sites by surface nitrates[8,9];the fast SCR activity of NO/NO2–NH3is similar to the activity of NH3+NO in the absence

of gaseous NO2but in the presence of either NH4NO3[6,7,10]or nitrates prestored onto the vanadium catalyst surface[8,9].This rules out the possibility that the fast SCR reaction(2)can proceed in parallel or consecutively to the nitrate decomposition by NO[re-action(6)].

There is now a trend in the automobile industry to replace vanadium-based SCR catalysts with zeolite-based systems to ex-pand the operating temperature window and address the problems associated with high-temperature deactivation of the anatase–rutile TiO2transition.Zeolites are the new class of automotive SCR catalysts.Various zeolites have been proposed for this purpose,in-cluding ZSM-5,mordenite,beta,ferrierite,and Y-zeolite[11].In the most active systems,zeolites generally are promoted by transition metals,such as iron,copper,and silver.These catalysts reportedly are associated with good deNO x activity in the standard and espe-cially the fast SCR reactions[11–17].

Concerning the mechanistic features of fast SCR over zeolites, Weitz et al.[18]proposed a fast SCR pathway over a BaNa–Y ze-olite similar to that discussed above for V2O5–WO3/TiO2catalysts,based on spectroscopic evidence and on steady-state reaction data. In addition,other authors have reported NO2disproportion[19–21] and ammonium nitrate formation[16,22]over promoted and un-promoted zeolites.Based on the analysis of their own data and of literature data,Kr?cher et al.[23]recently proposed a com-mon SCR reaction scheme for transition–metal zeolites and for vanadium-based catalysts that is in close agreement both with the chemistry over a V2O5–WO3/TiO2catalyst reported in our previous work[6,7]and with the scheme proposed for the BaNa–Y zeo-lite[18].

Herein we present a dedicated investigation of the elemen-tary steps of the fast SCR reaction at low temperature over the same commercial Fe-ZSM5catalyst used in a previous SCR reac-tivity study[26].Our goal is to assess and critically evaluate the current ideas on the SCR mechanism,and speci?cally to estab-lish in a conclusive manner to what extent the same mechanistic pathways demonstrated for V-based catalysts also apply to Fe-promoted zeolite catalysts under fully representative conditions for automotive applications.For this purpose,we take the same ex-perimental approach(transient reaction experiments)used in our previous mechanistic investigation over V2O5–WO3/TiO2,in order to establish a direct link to the results for V-based catalysts.

2.Experimental

The commercial catalyst used in this work was originally sup-plied by Daimler in the form of a cordierite honeycomb mono-lith(400cpsi—6.5mils)washcoated with Fe-ZSM5.For testing, the catalyst was crushed and sieved to140–200mesh,to avoid mass transfer limitations.Samples(160mg of catalyst powder or 80mg of catalyst powder diluted with80mg of quartz pow-der)were loaded into a?ow-microreactor consisting of a quartz tube(6mm i.d.)placed in an electric furnace.The reaction tem-perature was monitored and controlled by a K-type thermocouple immersed in the catalyst bed.Mass-?ow controllers(Brooks In-struments)were used to dose He,Ar,NH3,NO,NO2,and O2in the gaseous feed stream,while water vapor was added via a saturator operated at controlled temperature.All of the lines before and af-ter the reactor were heated to200?C to prevent H2O condensation and NH4NO3deposition.The species concentrations in the outlet stream were continuously monitored by a quadrupole mass spec-trometer(Balzer QMS200)and a UV analyzer(ABB-LIMAS11HV) in parallel.He was used as carrier gas to enable evaluation of N balances at steady state.More experimental details are available elsewhere[5,7,8,26].

Before the experiments,the catalyst was conditioned with a temperature ramp of10?C/min up to600?C in2%O2v/v,then held at600?C for1h.Transient runs consisted of step-response experiments at150–170–190?C(transient response method[TRM]) and in temperature-programmed reaction(TPR)runs.In a typical TRM run,the reactor was kept at constant temperature under a ?ow of He+1%H2O,and step changes(e.g.,0→1000→0ppm or0→500→0ppm)of feed NH3or NO or NO2concentra-tions were imposed.TRM tests were carried out over diluted cat-alyst beds at72or140cm3/min(STP),corresponding to GHSV= 8600–23,000h?1if referred to a monolith catalyst.At the end, a temperature ramp(10?C/min,T end=550?C)was run to clean up the catalyst surface.In the TPR runs,a stream containing NH3

(1000ppm)and NO x(1000ppm,with NO/NO x=1or0.5)with O2(0or2%v/v)and H2O(1%v/v)in He was fed to the reactor initially at150?C,and then the reactor temperature was linearly increased up to550?C at a heating rate of20?C/min.Because the purpose of this work was to address the chemistry of the fast SCR reaction(2),many runs were performed in the absence of O2so as to eliminate contributions of the standard SCR reaction(1).

314 A.Grossale et al./Journal of Catalysis 256(2008)

312–322

Fig.1.Formation of ammonium nitrate over the Fe-ZSM5catalyst.W cat =0.080g,?ow rate =140cm 3/min (STP).Feed =1%H 2O,2%O 2,1000ppm NH 3and 1000ppm NO 2+He.T =180?C.

Additional NO 2adsorption runs were performed to study the formation of surface nitrates and NH 4NO 3over undiluted crushed monolith samples at 120cm 3/min (STP).A few ?nal runs with step changes in the NH 3feed were devoted to study the fast SCR dynamics over Fe-ZSM5at 200?C using a higher feed ?ow rate (240cm 3/min STP)in the presence of O 2(2%),to extend the study to conditions closer to automotive applications.3.Results and discussion 3.1.NH 4NO 3formation

Fig.1shows a transient run at 180?C addressing the forma-tion of ammonium nitrate over Fe-ZSM5.After the catalyst was saturated with NH 3(1000ppm),at time t =0s NO 2(1000ppm)was added stepwise to the feed stream.At steady state,the data indicate equal conversions of NO 2and NH 3( NO 2= NH 3=750ppm),the formation of N 2(380ppm),of N 2O (20ppm),and a lack of about 700ppm in the overall N balance (total atomic N =1300ppm).These results agree with the stoichiometry of re-action (3)and correspond to the formation of about 350ppm of NH 4NO 3,which,of course,cannot be detected by our analyzers.In previous work [6,7,10],we found similar behavior (except for N 2O formation)over a V 2O 5–WO 3/TiO 2catalyst and also documented that part of the NH 4NO 3was decomposed to HNO 3+NH 3and es-caped undetected from the reactor,later condensing in cold spots along the downstream lines.

As discussed above,in the case of V-based catalysts and BaNa–Y zeolites,the formation of ammonium nitrate has been attributed in the past to NO 2dimerization and disproportion [reactions (7)and (8)],coupled with the formation and decomposition of ammo-nium nitrite [reaction (9)]and the reaction between nitric acid and ammonia [reaction (10)].We addressed the question as to whether the same mechanism also applies to Fe-ZSM5by means of two NO 2adsorption experiments conducted at 150?C in the absence and presence of preadsorbed NH 3(Figs.2A and 2B ).Both runs con-sist of a step addition of NO 2only (1000ppm at t =0s)to a feed stream containing 1%H 2O,2%O 2,and He ?owing over either a clean Fe-ZSM5catalyst or a catalyst sample previously exposed to NH 3at 150?C.

Fig.2A shows storage of NO 2onto the catalyst up to saturation in the absence of preadsorbed ammonia,accompanied by evolution of NO.The data,reported previously [26],are consistent with 3NO 2+H 2O ?NO +2HNO 3.

(12)

Note that the molar ratio NO/ NO 2is approximately equal to 1/3during the entire adsorption transient.The overall reaction (12)actually describes the chemisorption of NO 2in the form of ni-trates and results from the combination of the NO 2dimerization and disproportion reactions [reactions (7)and (8)]and the oxida-tion of nitrite species by NO 2[reaction (11reverse )].Accordingly,the results of Fig.2A agree with the proposed chemistry and with IR studies documenting the formation of nitrates on zeolite cata-lysts on exposure to NO 2[18,24,25].Kr?cher and co-workers also demonstrated reaction (12)in relation to NO 2adsorption onto Fe-ZSM5[22]and Cu-ZSM5[21].

When the same NO 2storage experiment was run in the pres-ence of ammonia preadsorbed on the catalyst,however,evolution of N 2instead of NO was observed,as shown in Fig.2B.Remark-ably,the N 2concentration detected during the initial stage of the reaction amounted to about 500ppm versus a total conversion of the 1000ppm of NO 2in the feed.This corresponds to the overall stoichiometry of ammonium nitrate formation from NO 2and ad-sorbed ammonia [reaction (3)],according to steps (7)–(10),which involve disproportion of NO 2[reactions (7)and (8)],as shown in Fig.2A,but in this case followed by reaction of nitrites with NH 3rather than with NO 2and leading to N 2via ammonium nitrite de-composition [reaction (9)].As a further con?rmation,we note that the total amount of N 2evolved during the experiment in Fig.2B (≈0.2mmol /g)was close to the amount of preadsorbed ammo-nia (≈0.18mmol /g),as would be expected from (9).A TPD run at the end of the NO 2storage phase demonstrated no N 2O evolu-tion,thus con?rming that no NH 4NO 3was left on the catalyst.On the other hand,the NO 2evolution from nitrate decomposition was similar to that observed during the corresponding ?nal TPD part of the run shown in Fig.2A.

Comparing the chemistry involved in NO 2adsorption onto Fe-ZSM5in the absence and in the presence of adsorbed ammo-nia reveals that at 150?C surface nitrites (or nitrous acid)react more readily with NH 3according to the ammonium nitrite forma-tion/decomposition reaction (9)rather than with NO 2according to the reverse of (11),the reaction observed in the absence of am-

A.Grossale et al./Journal of Catalysis256(2008)312–322

315

Fig.2.Effect of preadsorbed NH3on NO2storage on Fe-ZSM5.W cat=0.160g,?ow rate=120cm3/min(STP).Feed=1%H2O,2%O2,NO2=1000ppm+He.T=150?C. A=clean catalyst.B=catalyst with preadsorbed NH3.

monia.This reaction is indeed very fast;complete oxidation of nitrous acid by NO2occurs already at150?C,as indicated by the stoichiometry observed during NO2adsorption on the clean cata-lyst(see Fig.2A and related discussion).Other data(not reported) show the same behavior already at50?C.Thus,the preferential re-action of nitrites with ammonia,even if their oxidation by NO2 is so facile,merits some consideration.Our data also indicate that ammonia reacts preferentially with surface nitrites,thus forming N2,rather than with nitrates to form NH4NO3.

3.2.Reactivity of NH4NO3with NO

To investigate the reactivity of NH4NO3with nitric oxide over Fe-ZSM5,ammonium nitrate was generated in situ(i.e.,on the cat-alyst itself).As shown in Fig.3,1000ppm of NO2along with H2O (1%v/v)and O2(0%v/v)were initially fed to the microreactor at 170?C;subsequently,1000ppm of NH3was added to the feed to form and build up ammonium nitrate on the catalyst surface ac-cording to reaction(3).At the end of the?rst build-up stage,only NO2was removed from the feed stream while NH3was retained, to limit decomposition of ammonium nitrate to NH3+HNO3,thus preserving a signi?cant fraction of the ammonium nitrate formed

on the catalyst.In the?nal stage of the run,1000ppm of NO was added to the NH3-containing feed stream,still without oxygen.The same experimental procedure has been used previously to study the reactivity of NH4NO3with nitric oxide over V2O5–WO3/TiO2 [6,7].

Fig.3shows the temporal evolutions of the outlet concen-trations of NH3,NO,NO2,N2,and N2O during the NH4NO3 buildup and reactivity run over Fe-ZSM5.During the?rst stage (t<7600s),when NH3and NO2were co-fed to the reactor, a roughly equimolar consumption of both species was observed ( NO2=830ppm; NH3=820ppm),along with formation of 430ppm of N2,15ppm of N2O,and a lack of760ppm in the N balance(total atomic N=1240ppm).Such results are clearly in line with the formation of ammonium nitrate[reaction(1)], as discussed in the previous section,and point to the forma-tion/deposition of NH4NO3salt onto the catalyst surface.A small fraction of such ammonium nitrate was decomposed to N2O.The formation of NH4NO3salt on V2O5–WO3/TiO2under similar con-ditions has been documented by IR analysis of a catalyst sample unloaded from the reactor[10].

After the NO2feed was shut off,the ammonia concentration level returned to its feed value,and the concentrations of all the other species dropped to zero.This indicates that no reaction oc-curred between ammonia and ammonium nitrate at this temper-ature[6,7,10].At t=9600s,NO(1000ppm)was added to NH3 in the feed,which resulted in a long transient(prolonged un-til t≈13,000s),associated with the conversion of NO and NH3 and the formation of N2and NO2.The conversion ratio of NO and NH3was1:1during the entire transient period except the initial 600s,when a higher NO consumption along with formation of a few ppm of NO2were seen.The evolution of nitrogen mirrored the consumption of NO and NH3but exceeded it signi?cantly(e.g., NO=90ppm, NH3=100ppm,N2=130ppm).

The reactivity observed when NH3and NO were co-fed to the Fe-ZSM-5catalyst cannot be explained by the standard SCR re-action(1),which exhibits a different stoichiometry and requires the participation of O2.Rather,it is attributed to the reaction(6) between NO and the ammonium nitrate deposited onto the cat-alyst during the previous stage of the experiment.Under similar operating conditions,we observed the same behavior over a V2O5–WO3/TiO2catalyst;we explain this as due to the following reac-tion:

NH3+NO+

NH4NO3→

N2+

H2O.(13)

In view of the1:1consumption ratio between NO and NH3,along with the formation of about3/2ppm of N2for each ppm of con-verted NO observed over Fe-ZSM5,reaction(13)also explains the results shown in Fig.3.Notably,reaction(13)is simply the sum of reaction(6)between NO and ammonium nitrate,forming NO2, and reaction(3)between such NO2and NH3,which rapidly re-forms part of the converted ammonium nitrate.

Additional runs to explore the temperature dependence of the reactivity of NH4NO3with NO were performed at150and190?C (Figs.4A and4B).At both temperatures,the Fe-ZSM5catalyst was active in the formation of ammonium nitrate[reaction(3)],con-?rming the expected stoichiometry within experimental error.An increase in the associated NO2and NH3conversions was observed with decreasing temperature,indicating that NH4NO3formation is favored by low temperatures,in agreement with the litera-ture[1,18].As for the reaction between ammonium nitrate and NO+NH3,no conversion was apparent at150?C(Fig.4A),whereas considerable reactivity was detected at190?C(Fig.4B).In fact,in

316 A.Grossale et al./Journal of Catalysis 256(2008)

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Fig.3.Buildup of ammonium nitrate and its reactivity with NO over Fe-ZSM5.W cat =0.080g,?ow rate =72cm 3/min (STP).Feed =1%H 2O,0%O 2,NH 3=0–1000ppm,NO =0–1000ppm,NO 2=0–1000ppm +He.T =170?C.

the latter case,an initial evolution of 450ppm of N 2was found,which is in fair agreement with reaction (13)( NO =320ppm)but far greater than the 130ppm of N 2observed in the run at 170?C (Fig.3).

Based on the aforementioned ?ndings,it seems legitimate to conclude that a similar reactivity between NO and ammonium nitrate applies over the present Fe-ZSM5catalyst,as has been reported previously for V 2O 5–WO 3/TiO 2catalysts and a BaNa–Y zeolite [6,7,18,23].The results shown in Fig.3and the related in-terpretation also agree with the IR data of Busca et al.[25],who studied the interaction of NO and NO/NO 2with NH 3preadsorbed onto H-ZSM5and found that NO 2reacted readily at room temper-ature with adsorbed ammonium ions,forming nitrates and N 2,as expected from reaction (3),whereas in the presence of NO +NO 2,the catalyst was completely depleted of adsorbed ammonia and of nitrates at 373K,consistent with the reduction of nitrates by NO [reaction (11)]and the resulting overall reaction (2).Furthermore,the present data demonstrate a strong temperature dependence of reaction (6)between NO and NH 4NO 3.3.3.Role of NH 4NO 3in the fast SCR reaction

After demonstrating the reactivity of NH 4NO 3with NO over Fe-ZSM5,we proceeded to study the relationship of such a reaction with the NO/NO 2–NH 3(fast SCR)reacting system.In analogy with our previous studies on a V-based catalyst [6,7],the study relied on TRM runs involving a ?rst stage in which NH 3,NO,and NO 2(1000:500:500ppm)were co-fed to the Fe-ZSM5catalyst along with H 2O (1%v/v)but with no O 2,followed by a second stage after stepwise removal of NO 2from the feed stream.

Fig.5displays the dynamics of the NH 3,NO,NO 2,N 2,and N 2O outlet concentrations observed during one of such runs at 170?C.At t >3000s,when NO and NO 2were added to NH 3in the feed,a reaction transient associated with conversion of both NH 3and NO x and with the formation of N 2and of a few ppm of N 2O be-came apparent.At steady state,the NH 3consumption was around 440ppm,close to the NO x conversion of 460ppm.It should be noted,however,that the NO 2conversion was much greater than the NO conversion ( NO =40ppm, NO 2=420ppm);therefore,the fast SCR reaction (2)by itself cannot explain the observed be-havior,because it would result in equimolar conversions of NO and NO 2.In view of the low temperature (170?C)and of the higher NO 2conversion,it is then reasonable to propose that also reac-tion (3)(i.e.,formation of ammonium nitrate)also was proceeding along with the fast SCR reaction (2).The formation of NH 4NO 3is in fact corroborated by a lack in the atomic nitrogen balance at steady state;furthermore,it is compatible with the observed N 2concentrations,as we brie?y discuss in what follows.

We consider the NO consumption ( NO =40ppm)to rep-resent the extent of the fast SCR reaction (2),whereas the ex-tent of reaction (3)is obtained by subtracting the amount of NO converted by the fast SCR reaction from the total NO 2conver-sion:( NO 2Amm =420?40=380ppm).Accordingly,the total N 2formed by reactions (2)and (3)should amount to 80+190=270ppm,which is close enough to the 280ppm of nitrogen ac-tually detected at steady state.Furthermore,the observed lack of 320ppm in the atomic N balance is compatible with the ex-pected formation of approximately 180ppm of NH 4NO 3due to reaction (3),after subtracting 10ppm of N 2O from the NH 4NO 3decomposition.Based on these ?ndings,we therefore propose that both reactions (2)and (3)occurred during the ?rst stage of the transient run in Fig.5,with the formation and deposition of am-monium nitrate on Fe-ZSM5.Again,the same behavior had been reported previously under similar conditions over V 2O 5–WO 3/TiO 2and zeolite catalysts [4,6,7,10,21,26].

We now examine the second stage of the TRM run in Fig.5.When NO 2was removed from the feed stream at t ≈13,000s,a discontinuity in the outlet concentration traces of all species but NO became apparent.In fact,the ammonia concentration rose to about 960ppm,the NO 2trace dropped rapidly to zero,the N 2concentration decreased to about 60ppm (mirroring the NH 3evolution),and the NO outlet concentration remained unaltered at 460ppm.For pseudo steady-state conditions,such data imply similar consumption of NO and NH 3(about 40ppm)and a simul-taneous formation of 60ppm of N 2,demonstrating a stoichiometry similar to that reported earlier for the reaction between NO and NH 4NO 3[reaction (6)].In other words,during this second stage of the experiment,NO was reacting with the ammonium nitrate de-posited onto the catalyst for the duration of the ?rst stage.The resulting transient lasted about 6000s and in fact ended after de-pletion of all of the previously accumulated ammonium nitrate.

We now analyze in more detail the chemistry before and after NO 2was removed from the feed.We have shown that the conver-sion of NO was due to the fast SCR reaction (2)when NH 3,NO,and

A.Grossale et al./Journal of Catalysis256(2008)312–322

317

Fig.4.Effect of temperature on the buildup of ammonium nitrate and its reactivity with NO over Fe-ZSM5.W cat=0.080g,?ow rate=72cm3/min(STP).Feed=1%H2O, 0%O2,NH3=0–1000ppm,NO=0–1000ppm,NO2=0–1000ppm+He.T=150?C(A),190?C(B).

NO2were co-fed to the Fe-ZSM5catalyst.In contrast,in the sub-sequent stage,in the absence of NO2,NO consumption was due to reaction(6)between NO and ammonium nitrate.But despite the occurrence of two formally different reactions,the experimental concentration trace of NO shown in Fig.5demonstrates no discon-tinuity between the two stages on the stepwise removal of NO2 from the feed stream.However,recalling that in the presence of NH3,NO,and NO2(?rst stage in Fig.5),the formation of ammo-nium nitrate[reaction(3)]was already active along with the fast SCR reaction(2),this apparent contradiction can be explained by considering that during the?rst stage of the run,NO consumption occurred not directly at the expense of gaseous NO2[i.e.,according to reaction(2)],but rather via reaction of NO with NH4NO3[i.e., according to reaction(6)],with ammonium nitrate in turn formed from NO2and NH3according to reaction(3).This obviously ex-plains the absence of any discontinuity of the NO trace between the two parts of the experiment shown in Fig.5and points to a sequential scheme for the fast SCR chemistry in which ammonium nitrate(or a related surface species)plays the role of the key in-

termediate and reaction(6)between NO and ammonium nitrate is

the rate-determining step at these low temperatures.In particular,

we emphasize that the data shown in Fig.5demonstrate the occur-

rence of the fast SCR in the absence of gaseous NO2and rule out

signi?cant contributions to deNO x activity from a direct gas-phase

reaction between NO and NO2[16].These conclusions regarding

the fast SCR chemistry over Fe-ZSM5are in close agreement with

our previous?ndings for a V2O5–WO3/TiO2catalyst[6,7].

We further investigated the role of reaction(6)between

NH4NO3and NO in the fast SCR chemistry over the Fe-zeolite at

other temperatures,150and190?C;the results are shown in Fig.6. At the end of the?rst stage of the TRM run at150?C(Fig.6A),we observed no conversion of NO and equimolar conversions of NH3

and NO2( NH3=410ppm, NO2=405ppm),resulting in the evolution of200ppm of N2and a lack of400ppm in the N bal-

ance.These data indicate the occurrence of reaction(3)(formation

of ammonium nitrate)only,whereas the absence of NO conver-

318 A.Grossale et al./Journal of Catalysis 256(2008)

312–322

https://www.wendangku.net/doc/a010365537.html,parison between activity of fast SCR and activity of NO +NH 4NO 3over Fe-ZSM5.W cat =0.080g,?ow rate =72cm 3/min (STP).Feed =1%H 2O,0%O 2,NH 3=0–1000ppm,NO =0–500ppm,NO 2=0–500ppm +He.T =170?C.

sion is explained by the adverse effect of low temperature on the reactivity between NO and NH 4NO 3,as discussed previously (see Fig.4A).In fact,no reactivity of NO was detected during the sub-sequent transient phase after NO 2was removed from the feed.

In contrast,the ?rst stage of the TRM run at 190?C (Fig.6B)re-sulted in high equimolar conversions of NH 3and NO x (about 95%)associated with higher consumption of NO 2compared with NO ( NO 2=500ppm, NO =445ppm),formation of 915ppm of N 2,and a lack of about 40ppm in the atomic N balance.Within the limits of experimental error,such data are again consistent with the simultaneous occurrence of ammonium nitrate formation (3)and the fast SCR reaction (2),although with a much greater con-tribution of the latter than occurred at 170?C.This ?nding is ex-plained by the strong promoting effect of temperature on the key reaction (6)between NO and NH 4NO 3documented in Figs.3and 4.

The subsequent TRM stage,run at 190?C after NO 2removal,demonstrated signi?cant conversion of NO and NH 3,but only dur-ing an initial short transient phase.This ?nding is linked to the high fast SCR activity and the low NH 4NO 3production observed during the preceding stage in the presence of NH 3,NO,and NO 2.Accordingly,at 190?C,the system was unable to build up a sub-stantial amount of ammonium nitrate on the catalyst for its sub-sequent reaction with NO in the absence of NO 2,thus con?rming the importance of NH 4NO 3in the NO–NO 2/NH 3chemistry at low temperatures.

3.4.NH 3inhibition of NO reactivity with nitrates

Additional interesting information can be extracted from the ?nal part of the TRM run at 150?C.As shown in Fig.6A,imme-diately after the NH 3feed was shut off (t >24,000s),a peak of deNO x activity involving conversion of NO,formation of N 2,and evolution of NO 2appeared.The transient exhibited two dis-tinct phases.In the ?rst phase,NO conversion was associated with equimolar formation of N 2and NO 2,consistent with reaction (6)between NO and the residual ammonium nitrate on the catalyst surface,

NH 4NO 3+NO →N 2+NO 2+2H 2O.

(6)

In the second phase,however,the outlet concentration of N 2was greater than that of NO 2.This can be explained by a further re-action of NO 2from reaction (6)with NH 3still adsorbed onto the

catalyst according to reaction (3).Thus,the behavior observed at the time of ammonia shutoff is consistent with the overall fast SCR chemistry proposed over Fe-ZSM5,but apparently contradicts the temperature threshold of 150?C observed for the onset of re-action (6)between NH 4NO 3and NO.A possible reason for this ?nding is that reaction (6)actually may occur between NO and ni-tric acid (or surface nitrates)[see reaction (11)]formed by NH 4NO 3decomposition according to reaction (10reverse),and then would be inhibited by NH 3.Reducing the gaseous ammonia concentra-tion would shift the equilibrium of NH 4NO 3decomposition toward higher HNO 3concentrations,thereby promoting the reactivity with NO.A similar effect was observed at different temperatures as well.The formation of surface nitrates and their role in the formation of ammonium nitrate were already demonstrated in this work by the NO 2adsorption experiments (see Fig.2).Ammonia inhibition of reaction (6)over V 2O 5–WO 3/TiO 2also has been proposed [6,7].3.5.TPR experiments

More information con?rming the central role of nitrates in the fast SCR reactivity is provided in Fig.7,which compares the tem-perature dependence of NO conversion measured during four dif-ferent NO +NH 3TPR experiments with equal space velocities and heating rates (20K /min).In the experiment re?ected in curve A,the feed included NO +NH 3(1000ppm each)+H 2O (1%v/v),but no oxygen.As expected,the observed temporal evolution of the outlet concentrations,indicating the onset of deNO x activity only above 300?C,is in agreement with the so-called “slow”SCR reac-tion [4],that is,the poorly active deNO x reaction between NO and NH 3in the absence of oxygen,3NO +2NH 3→

N 2+3H 2O .

(14)

Repeating the same temperature ramp experiment but with 2%O 2v/v in the feed (curve B)revealed greater deNO x activity,due to the standard SCR reaction (1)instead of reaction (14).Curve C shows the even much higher deNO x activity resulting from running the same temperature ramp with a feed containing 1000ppm of NH 3and 500ppm each of NO and NO 2.Of course,curve C is represen-tative of the NO conversion in the fast SCR reaction (2).During the fourth and ?nal TPR experiment,associated with curve D,a feed containing NO +NH 3(1000ppm each)+H 2O (1%v/v),but no

A.Grossale et al./Journal of Catalysis256(2008)312–322

319

https://www.wendangku.net/doc/a010365537.html,parison between activity of fast SCR and activity of NO+NH4NO3over Fe-ZSM5:effect of temperature.W cat=0.080g,?ow rate=72cm3/min(STP).Feed=1% H2O,0%O2,NH3=0–1000ppm,NO=0–500ppm,NO2=0–500ppm+He.T=150?C(A),190?C(B).

oxygen or NO2,was passed over a catalyst sample preexposed to 1000ppm of NO2+1%H2O at60?C.Fig.7shows that during the initial part of this temperature ramp,up to about200?C,the evo-lution of the NO conversion matched that seen for the fast SCR TPR run.As the experiment proceeded,NO conversion dropped sharply, reaching close to zero,before eventually approaching the behavior observed for the slow SCR reaction(curve A).

Recalling the data on the buildup of nitrates on the Fe-ZSM5 catalyst on NO2adsorption(see Fig.2),a likely explanation of the similarity between the initial parts of curves C(fast SCR) and D(NO+NH3over catalyst pretreated with NO2)in Fig.7is that in both cases,NO and ammonia in the feed were reacting with surface nitrates,either formed directly via NO2disproportion (curve C)or formed previously and stored on the catalyst during its pretreatment with NO2(curve D).Notably,once again in this experiment,the deNO x activity in the absence of gaseous NO2but the presence of surface nitrates was virtually identical to that as-sociated with the fast SCR reaction up to about200?C.The drop in NO conversion shown by curve D at temperatures above200?C can be attributed to the depletion of surface nitrates.In fact,in another similar experiment(not reported),in which the catalyst was pretreated with NO2at150?C rather than at60?C,an earlier drop of the NO conversion occurred,due to the reduced amount of nitrates stored at the higher temperature.Eventually,the match between curves D and A at temperatures above300?C con?rms the absence of any residual oxidizing agents in the?nal part of the temperature ramp experiment over the NO2-pretreated sam-ple.

Based on the data presented and discussed so far,the reac-tivity of NO/NO2–NH3over Fe-ZSM5at low temperatures appears to be totally consistent with earlier?ndings over vanadium-based catalysts[6,7,23]as well as with the mechanistic proposals for

320 A.Grossale et al./Journal of Catalysis 256(2008)

312–322

Fig.7.Temperature-programmed reaction experiments over Fe-ZSM5.W cat =0.080g,?ow rate =72cm 3/min (STP).Curve A (slow SCR):Feed =1%H 2O,0%O 2,NH 3=1000ppm,NO =1000ppm +He.Curve B (standard SCR):Feed =1%H 2O,2%O 2,NH 3=1000ppm,NO =1000ppm +He.Curve C (fast SCR):Feed =1%H 2O,0%O 2,NH 3=1000ppm,NO =500ppm,NO 2=500ppm +He.Curve D:Feed =1%H 2O,0%O 2,NH 3=1000ppm,NO =1000ppm +He over catalyst pretreated with NO 2(1000ppm)+H 2O (1%)at 60?

Fig.8.Fast SCR:TRM run over Fe-ZSM5.W cat =0.100g,?ow rate =240cm 3/min (STP).Feed =1%H 2O,2%O 2,NH 3=0–1000ppm,NO =0–500ppm,NO 2=0–500ppm +He.T =200?C.

BaNa–Y [18],all of which depend on the reactivity between NO and ammonium nitrate or surface nitrates in the fast SCR chem-istry.Our ?ndings further demonstrate the similarity of the rate of the fast SCR reaction and the rate of nitrate reduction by NO,which had not been reported previously on zeolite catalysts.3.6.Fast SCR dynamics under NH 3pulsed feed

We analyzed the dynamic behavior of the NO/NO 2–NH 3re-acting system over Fe-ZSM5under a stepwise feed of ammonia at low temperature at conditions closer to those prevailing in real automotive SCR converters—namely in the presence of oxygen and at higher space velocities.Fig.8shows the temporal evo-lution of the outlet species concentrations during a TRM run at

200?C with 1000ppm of NH 3added to a feed stream contain-ing 500ppm of NO and 500ppm of NO 2with O 2(2%)and H 2O (1%).The data identify a ?rst transient phase with high deNO x ac-tivity that was,however,progressively reduced until steady state was reached,along with a ?nal phase after NH 3shutoff,again as-sociated with high deNO x activity,which was rapidly exhausted.Fig.8shows a simultaneous conversion of both NO and NO 2at steady state at the end of the ?rst phase,with NO 2consumption higher by about 100ppm,formation of N 2in amounts equal to 3/2of the NO consumption added to half of the NO 2consump-tion,and a lack of 100ppm in the N balance.Such behavior can be well explained by the chemistry discussed in the previous sec-tions,invoking ammonium nitrate formation [reaction (3)]and the consecutive reaction (6)between NO and NH 4NO 3.

A.Grossale et al./Journal of Catalysis 256(2008)312–322321

Somewhat different behavior can be observed in the second phase of the run shown in Fig.8.After stepwise removal of NH 3from the feed,a peak in NO conversion appeared,accompanied by evolution of N 2and of NO 2,which temporarily exceeded their feed concentrations of 500ppm.In analogy to the discussion of the ?nal stage in Fig.6A,such dynamics can be attributed to the reaction of NO with ammonium nitrate and to the inhibiting effect of ammonia.In fact,removing NH 3from the gas phase promoted reaction (6)between NO and NH 4NO 3still present on the cata-lyst,thereby releasing NO 2and N 2until the surface species was depleted.

More TRM runs at higher temperatures (225–300?C)(not re-ported)demonstrated higher activity,approaching total conversion of NO x .The reaction dynamics observed during the ?rst stage of the TRM runs,after the addition of NH 3to the feed stream,were qualitatively similar to the run shown in Fig.8,but transients were faster due to the higher deNO x activity.In contrast,the ?nal tran-sient phase after the removal of NH 3from the feed became shorter with increasing temperature,and eventually disappeared.This is consistent with the reduced storage of surface species (adsorbed NH 3and nitrates)at higher temperatures.

3.7.Rephrasing the reactions in terms of surface species

Throughout this paper,all of the reactions involved in the NO–NO 2/NH 3chemistry have been expressed conventionally in terms of molecular species.But,as is apparent from the data presented so far,the actual catalytic mechanism likely involves related sur-face adspecies,as discussed,for example,in the analysis of the data given in Figs.6and 7.Accordingly,HONO and HNO 3in the reaction steps should be replaced with nitrite and nitrate species,respectively.

Fig.9shows a schematic summary of the fast SCR chemistry in terms of surface species.The related basic reaction steps are given in Table 1,along with data on the decomposition of the overall reactions observed in this work.Thus,for example,the reaction sequence yielding the fast SCR reaction (2)can be rephrased in terms of the elementary steps in Table 1as

2NH 3+H 2O ?2NH +4+O

2?,R42NO 2+O 2??NO ?2+NO ?

3,R1+R2

NO ?3+NO ?NO 2+NO ?2,R72NH +4+2NO ?2→2N 2+4H 2O.

2*R5

4.Conclusion

Our ?ndings demonstrate conclusively that the chemistry pro-posed for the fast SCR reaction at low temperatures over V 2O 5–

WO 3/TiO 2[6,7,10,23]and over zeolite systems [13,18,22]is able to interpret the steady-state and dynamic features of the NO/NO 2–NH 3system over commercial Fe-ZSM5catalysts,as well under conditions representative of diesel exhaust after treatment,as pro-posed previously [23].Accordingly,the role of NO 2in the fast SCR reactivity is to form surface nitrites and nitrates via dimerization and disproportionation/heterolytic chemisorption,the role of NO is to reduce nitrates to nitrites,and the role of NH 3is to enable rapid and selective decomposition of nitrites to nitrogen via formation of unstable ammonium nitrite.It was pointed out previously that this chemistry can explain the optimal 1:1molar ratio of NO and NO 2in the fast SCR reaction [6,13,15].It also can explain the full range of selectivity resulting from varying the NO 2/NO x feed ra-tio [13,24,26];incomplete reduction of nitrates by NO (the critical step R7in Table 1)is responsible for the undesired formation of NH 4NO 3at very low temperatures and of N 2O at low to interme-diate temperatures.

Although the general SCR chemistry emerging from the present work essentially con?rms existing concepts,here for the ?rst time it has been evaluated over zeolite systems on a step-by-step basis by means of transient reaction analysis.Thanks to this powerful technique,additional novel results have been obtained over Fe-ZSM5:

1.The reduction of nitrates by NO (or,conversely,the oxida-tion of NO by nitrates)is the rate-limiting step in the fast SCR chemistry at low temperature;the reverse reaction (i.e.,oxidation of nitrites by NO 2)is very fast even at very low tem-

perature.

Fig.9.Proposed reaction scheme for NO/NO 2–NH 3SCR at low temperature.

Table 1

The fast SCR chemistry

Basic reaction steps in NO/NO 2–NH 3SCR chemistry over V-based and zeolite catalysts Involving NO 2only 2NO 2?N 2O 4

see (7)N 2O 4+O 2??NO ?2+NO ?

R2see (8)

NO 2+NO ?2?NO +NO ?

R3see (11reverse)

In the presence of NH 3

2NH 3+H 2O ?2NH +4+O

2?R4NH 3adsorption NH +4+NO ?

2?[NH 4NO 2]→N 2+2H 2O

R5see (9)NH +4+NO ?

3?NH 4NO 3

see (10)

In the presence of NO

NO +NO ?3?NO 2+NO ?

R7see (11)

Global reactions observed in this work,and their relationship with the basic reactions above 3NO 2+O 2??NO +2NO ?3

(12)=R1+R2+R32NO 2+2NH 3→NH 4NO 3+N 2+H 2O (3)=R1+R2+R4+R5NO +NH 4NO 3→NO 2+N 2+2H 2O

(6)=R6reverse +R7+R5

NO +NH 3+12NH 4NO 3→32N 2+52H 2

O (13)=(6)+12

(3)2NH 3+NO +NO 2→2N 2+3H 2O

(2)=R4+R1+R2+R7+2*R5

322 A.Grossale et al./Journal of Catalysis256(2008)312–322

2.Ammonia inhibits such a redox step,likely by blocking the

surface nitrates;high NH3concentrations have a detrimental effect on fast SCR kinetics at low temperature[26].

3.The same enhanced fast SCR deNO x activity also is seen in the

absence of gaseous NO2,provided that the catalyst has been saturated with nitrates.This important result is not obvious from the previous SCR literature.

In summary,our work emphasizes the key role of surface ni-trates in the fast SCR chemistry.Their reactivity with NO is critical to explaining the strongly enhanced deNO x activity and governs the fast SCR kinetics at low temperature,whereas their buildup and depletion controls the SCR dynamics in parallel to ammonia adsorption–desorption.Identifying the elementary steps of fast SCR reactions over the Fe-ZSM5catalyst is an important step in deriv-ing chemically consistent kinetic schemes,as well as a key stage in the development of new catalytic systems and integrated af-tertreatment technologies.

Acknowledgments

The authors thank one of the reviewers for critical suggestions that helped improve the quality of the paper.

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火灾自动报警系统工程施工组织方案

专业资料自动火灾报警系统施工方案（一）配管及管内穿线工程 1、总则认真消化、熟悉图纸，所有配管工程必须以设计图纸为依据，严格按图施工，不得随意改变管材质、设计走向主连接位置。如必须改变位置和走向，除在图上标示清楚外，同时办理有关变更手续。 2、暗配管需沿最近路线敷设，尽量减少弯头数。埋入墙和地面混凝土中的管个壁离结构表面的净距不应小于30 mm，进入落地式电柜的管线应排列整齐，高度一致，管口应高出基础面不小于50mm。 3、所有穿线钢管均采用冷弯法，弯曲半径暗配管不得小于其外径的10倍，明配管不得小于管外径的6倍。管材弯曲处严禁有折皱、凹凸、裂缝等现象，管子弯扁度不得大于管径的 10%。 4、管路长度超过一定距离时，管路中间应加装过路接线盒或把管径放大一级：管子长度每超过45m，无弯曲时；管子长度每超过30m，有一个弯曲时；管子长度每超过20m，有二个弯曲时；管子长度每超过12m，有三个弯曲时。 5、加装接线盒的位置奕便于穿线与检修维护，不宜在潮湿有腐蚀性介质场所加装接线盒。管子入盒时，盒外侧应套锁母，

内侧应装护口，在吊顶内敷设时，盒的内外侧均应套锁母。 6、管内或线槽的穿线，应在穿线前应将管、槽内的积水及杂物清除干净。 7、不同系统、不同电压等级、不同电流类别的线路，不应穿在同一管内或线槽的同一孔内。导线在管、槽内，不应有接头或扭结。导线的接头应在接线盒内焊接或用端子连接。敷设在地下室等潮湿或多尘场所管路的管口和管子连接处，均应作密封处理。（二）线槽安装 1、在吊顶内敷设的各类管路和线槽需采用单独的卡具吊装或支持物固定，不要依附在吊顶支架上。 2、线槽的直线段应每隔1.0~1.5m设置吊顶或支点。在下列部位也设置支、吊点：线槽接头处；距接线盒 0.2m处；线槽走向改变或转弯处。 3、吊装线槽的吊杆直径不小于6mm。 4、管线径过建筑物的变形缝（包括沉降、伸缩缝、抗震缝）处，应采取补偿措施。导线跨越变形缝的两侧应固定，并留有适当余量。 5、火灾自动报警系统导线敷设后，应对每路导线用 500兆欧表测量绝缘电阻，其对地绝缘电阻值不小于 20兆欧。（三）火灾自动触发装置

火灾自动报警系统的组成

1火灾自动报警系统的组成？答案：火灾自动报警系统是由触发器件、火灾报警装置、火灾警报装置以及具有其它辅助功能的装置组成的火灾报警系统。它能够在火灾初期，将燃烧产生的烟雾、热量和光辐射等物理量，通过感温、感烟和感光等火灾探测器变成电信号，传输到火灾报警控制器，并同时显示出火灾发生的部位，记录火灾发生的时间。 2火灾自动报警系统的基本形式？答案：根据现行国家标准《火灾自动报警系统设计规范》规定，火灾自动报系统的基本形式有三种，即：区域报警系统、集中报警系统和控制中心报警系统。 3什么是火灾报警装置和火灾警报装置？答案：①在火灾自动报警系统中，用以接收、显示和传递火灾报警信号，并能发出控制信号和具有其它辅助功能的控制指示设备称为火灾报警装置。 ②在火灾自动报警系统中，用以发出区别于环境声、光的火灾警报信号的装置称为火灾警报装置。它以声、光音响方式向报警区域发出火灾警报信号，以警示人们采取安全疏散、灭火救灾措施。4火灾自动报警设备一般常见故障有哪些？答案： (1)主电源故障。 (2)备用电源故障。 (3)探测回路故障。

(4)误报火警。 5消防监控员定期检查主要工作有哪些？答案： ①每日查报警控制器的功能，并填写系统运行和控制器日检登记表。 ②每季度应检测和试验报警系统的下列功能，并填写季检表。 ③每年对火灾自动报警系统的功能，应作下列检查和试验，并填写年检表。 ④探测器投入运行二年后，应每隔三年全部清洗一遍，并作响应阈值及其它必要的功能试验，合格的方可继续使用，不合格的严禁重新安装使用。 6消防系统的分类？答案： ①水消防系统 ②气体消防系统 ③泡沫灭火系统 7火灾自动报警系统的误报的种类？答案：误报分为危险性误报和安全性误报两种，所谓危险性误报是指火灾发生时生产大量的烟、温而不能使系统发生报警信号者，又称不报。所谓安全性误报是指无火灾的情况下报警，又称虚报。 8火灾自动报警系统减少误报的方法？答案：

浅析城市轨道交通消防系统

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城市轨道交通火灾自动报警系统和消防灭火系统

城市轨道交通火灾自动报警系统和消防灭火系统一、火灾自动报警系统 1、FAS的组成 FAS由火灾报警控制器、火灾探测器、手动报警按钮和声光报警器等组成。（1）火灾报警控制器火灾报警控制器是FAS的核心组成部分。火灾报警控制器的主要功能有为火灾探测器提供稳定的工作电源，监视探测器及系统自身的工作状态，接受、转换和处理火灾探测器输出的报警信号，进行声光报警，指示报警的具体部位及时间，执行相应的辅助控制等任务。（2）火灾探测器火灾探测器是能对火灾参数（如烟雾、温度、火焰辐射和气体浓度等）进行响应，并自动产生火灾报警信号的器件。火灾探测器一般有感温火灾探测器、感烟火灾探测器、感光火灾探测器、可燃气体探测器和复合式火灾探测器五种基本类型。（3）手动报警按钮手动报警按钮是以手动方式生成火灾报警信号，启动火灾自动报警系统的器件。（4）声光报警器声光报警器是FAS中用以发出区别于环境声、光的火灾警报信号的装置，如警铃、警笛等。声光报警器以声、光音响方式向报警区域发出火灾警报信号，以警示人们采取安全疏散和灭火救灾措施。 2、FAS的功能 FAS由设置在控制中心的中央监控管理级、车站（车站与车辆段）监控管理级、现场控制级，以及相关网络和通信接口等环节组成。FAS的功能可分为中央级、车站级和现场级三个层次功能。（1）中央级功能中央级功能主要是实现城市轨道交通全线各车站、区间隧道、控制中心大楼、车辆段和主变电所等下属所有区域范围内火灾的监视、报警、控制及其他系统的消防联动，在火灾发生时承担全线灭火指挥任务。

（2）车站级功能车站级功能主要是实现车站及相邻半个区间隧道范围内火灾的监视、报警、控制，以及其他系统的消防联动。车站级火灾报警控制器随时监控和接收各探测点的报警信号，可发出声光报警信号，并能自动或手动执行对有关消防设施的联动控制。模拟图形显示终端按照车站建筑平面分级、分区显示本站消防系统的详细信息，并能够实时打印、输出各种有关数据报告。闭路电视监控系统在车站站台、站厅等公共场所安装全方位的监视器，实时收集站内的视频信息，并反映到值班室的监控器上，由值班人员进行监控和处理。（3）现场级功能现场级功能主要是指火灾监控与报警设备的具体功能，如火灾探测器用于对站内设备用房、站厅、站台乘客公共区等进行火灾自动探测；手动报警器安装于站内乘客公共区、设备用房区域及地铁车厢内，以方便现场人员及时通报火灾。另外，为便于紧急报警，在站内乘客公共区及设备用房区域设置的消火栓箱上，以及区间隧道和站内轨道外侧所设的消火栓箱上，配置有紧急电话插孔。 3、FAS的主要设备。FAS的三级功能分别配有相应的设备，以实现其功能。（1）中央级设备中央级设备位于OCC内，包括两台用于监控全线FAS的图形控制计算机和一台火灾报警控制主机。图形控制计算机根据不同级别的登录密码，分为主图形控制计算机和备用图形控制计算机。FAS中央级设备接收并储存全线消防设备的主要运行状态，接收全线车站、车辆段、主变电所等的火灾报警信息并显示报警部位。（2）车站级设备车站级设备主要由FAS火灾报警控制盘、图形监视计算机和FAS联动控制盘组成。这些设备都集中设在车站控制室内，用于监视车站消防设备的运行状态，接收车站火灾报警信号，并显示报警区域，优先接收控制中心发出的消防救灾指令和安全疏散命令。通过车站火灾报警控制盘上的RS485数据接口或消防联动控制盘上的手动控制按钮，向环境与设备监控系统（building automatic system，BAS）发出模式指令并由该系统启动消防联动设备。（3）现场级设备。现场级设备主要包括火灾探测器和手动报警按钮等。

消防火灾自动报警系统资料整理

附录四—A 火灾自动报警系统施工安装质量记录

目录序资料名称编号页数号 1火灾自动报警系统质量保证资料核查表A-1 2技术交底记录3 3施工组织设计（方案）5 4开工报告6 5设备材料相关证件汇总表7 6设备开箱检查记录8 7材料检查记录9 8火灾自动报警系统配管、配线安装检查记录A-2 9火灾自动报警系统电缆敷设检查记录A-3 10消防配电线路敷设检查记录10 11火灾自动报警系统接地电阻测试记录A-4 12火灾自动报警系统绝缘电阻测试记录A-5 13火灾自动报警系统配管配线隐蔽验收记录A-6 14火灾自动报警系统电缆敷设隐蔽验收记录A-7 15火灾自动报警系统报警控制器安装检查记录A-8 16火灾自动报警系统联动控制器安装检查记录A-9 17火灾自动报警系统探测器安装检查记录A-10 18火灾自动报警系统手动报警按钮安装检查记录A-11

19火灾自动报警系统警报装置安装检查记录A-12 20火灾自动报警系统探测、报警点全点试验记录A-13 21火灾自动报警系统联动控制点全点试验记录A-14 22火灾自动报警系统调试报告A-15 23火灾自动报警系统自检报告A-16 24火灾自动报警系统试运行记录A-17 序资料名称编号页数号 25竣工报告12 26设备移交清单13

火灾自动报警系统质量保证资料核查表编号：工程名称建设单位施工单位核查日期类别项目份数核查情况前期图纸会审、技术交底记录1交底完毕设计变更、技术核定单施工组织设计（方案）1已编制开工报告1已编制出厂检验设备（材料）相关证件汇总表1相关证件齐全设备（材料）检查记录1检查记录齐全隐蔽验收记录配管配线隐蔽验收记录1记录齐全电缆敷设隐蔽验收记录1记录齐全消防配电线路隐蔽验收记录安装检查试验记录各类安装检查记录1检查记录齐全各类测试、试验记录1记录齐全调试报告1已调试自检报告1已自检运行记录1已填写竣工报告1已填写设备移交清单1已填写其他核查意见：经检查,报警资料符合规范要求.

火灾自动报警系统的设计及其重要性

火灾自动报警系统的设计及其重要性火灾自动报警系统探测火灾隐患，肩负安全防范重任，是智能建筑中建筑设备自动化系统（CBS）的重要组成部分。智能建筑中的火灾自动报警系统设计首先必须符合GB50116-98《火灾自动报警系统设计规范》的要求，同时也要适应智能建筑的特点，合理选配产品，做到安全适用、技术先进、经济合理。火灾自动报警系统一般分三种形式设计：区域火灾自动报警系统，集中火灾自动报警系统和控制中心报警系统。就智能建筑的基本特点，控制中心报警系统是最适用的方式。智能建筑中中火灾自动报警系统的设计要点是：根据被保护对象发生火灾时燃烧的特点确定火灾类型；根据所需防护面积部位；按照火灾探测器的总数和其他报警装置（如手报）数量确定火灾报警控制器的总容量；按划分的报警区域设置区域报警控制器；根据消防设备确定联动控制方式；按防火灭火要求确定报警和联动的逻辑关系；最后还要考虑火灾自动报警系统与智能建筑“3AS”（建设设备自动化系统、通信自动化系统、办公自动化系统）的适应性。 1 火灾探测器的设计选配火灾探测器是火灾自动报警系统对象分为感烟火灾探测器、感温火灾探测器、感光火灾烟温复合式火灾探测器以及气体火灾探测器，按其测控范围又可分为点型火灾探测器和线型火灾探测器两大类。点型火灾探测器只能对警戒范围中某一点周围的温度、烟等参数进行控制，如点型离子感、点型紫光火焰火灾探测器、点型感温火灾探测器等，线型火灾探测

器则可以对警戒范围中某一线路周围烟雾、温度进行探测，如红外光束线型火灾探测器，激光线型火灾探测器，缆式线型感温火灾探测器等.

智能建筑中应以感烟火灾探测器选用为主，个别不宜选用感烟火灾探测器的场所，应该选用感温火灾探测器。 1.2 探测区域探测器设置要点标准规定：火灾探测区域一般以独立的房间划分探测区域内的每个房间内至少应设置一只探测器。在敞开或封闭的楼梯间、消防电梯前室、走道、坡道、管道井、闷顶、夹层等场所都应单独划分的探测区域，设置相应探测器、内部空间开阔且门口有灯光显示装置的大面积房间可划分一个的探测区域，但其最大面积不能超过1000m2。探测器的设置一般按保护面积确定，每只探测器保护面积和保护半径确定，要考虑房间高度、屋顶坡度、探测器自身灵敏度三个主要因素的影响，但在有梁的顶棚上设置探测器时必须考虑到梁突出顶棚影响另外，在设置火灾探测器时，还要考虑智能建筑内部走道宽度、至端墙的距离、至墙壁梁边距离、空调通风口距离以及房间隔情况等的影响。 1.3 探测器总数确定首先确定一个探测区域所需设置的探测器数量，其计算公式为： N=S÷KA 式中：N —探测器数量（只），取整数；

【智能楼宇自动化专业技术工作总结】智能楼宇自动化技术

【智能楼宇自动化专业技术工作总结】智能楼宇自动化技术智能楼宇自动化专业技术工作总结回眸过去，在xxx公司智能楼宇自动化工程师工作岗位上，我始终秉承着“在岗一分钟，尽职六十秒”的态度努力做好楼宇自动化工程师岗位的工作，并时刻严格要求自己，摆正自己的工作位置和态度。在各级领导们的关心和同事们的支持帮助下，我在智能楼宇管理师工作岗位上积极进取、勤奋学习，认真圆满地完成今年的智能楼宇管理师所有工作任务，履行好xxx公司自动化工程师工作岗位职责，各方面表现优异，得到了领导和同事们的一致肯定。现将工作岗位上的学习、工作情况作简要总结如下：智能楼宇管理师一、思想上严于律己，不断提高自身修养智能楼宇管理师一年来，我始终坚持正确的价值观、人生观、世界观，并用以指导自己在岗位上学习、工作实践活动。虽然身处在自动化工程师工作岗位，但我时刻关注国际时事和中央的精神，不断提高对自己故土家园、民族和文化的归属感、认同感和尊严感、荣誉感。在工作岗位上认真贯彻执行中央的路线、方针、政策，尽职尽责，在岗位上作出对国家力所能及的贡献。智能楼宇管理师二、工作上加强学习，不断提高工作效率智能楼宇管理师

时代在发展，社会在进步，信息技术日新月异。自动化工程师工作岗位相关工作也需要与时俱进，需要不断学习新知识、新技术、新方法，以提高岗位的服务水平和服务效率。特别是学习自动化工程师工作岗位相关法律知识和相关最新政策。唯有如此，才能提高工作岗位的业务水平和个人能力。定期学习岗位工作有关业务知识，并总结吸取前辈在工作岗位的工作经验，不断弥补和改进自身在工作岗位工作中的缺点和不足，从而使自己整体工作素质都得到较大的提高。智能楼宇管理师智能楼宇管理师回顾过去在工作岗位工作的点点滴滴，无论在思想上，还是工作学习上我都取得了很大的进步，但也清醒地认识到自己在岗位相关工作中存在的不足之处。主要是在理论学习上远不够深入，尤其是将思想理论运用到自动化工程师工作岗位的实际工作中去的能力还比较欠缺。在以后的岗位工作中，我一定会扬长避短，克服不足、认真学习工作岗位相关知识、发奋工作、积极进取，把工作做的更好，为实现中国梦努力奋斗。宇智能楼宇管理师展望未来，在以后的工作中希望能够再接再厉，要继续保持着良好的工作心态，不怕苦不怕累，多付出少抱怨，做好自动化工程师的本职工作。同时也需要再加强锻炼自身的工作水平和业务能力，在以后的工作中我将加强与同事多沟通，多探讨。要继续

火灾自动报警系统图集

第一章火灾自动报警系统说明典型火灾探测器的安装说明： 1.探测器至墙壁、梁边的水平距离不应小于0.5m。 2.探测器周围0.5m内不应有遮挡物。 3.探测器至空调送风口边的水平距离，不应小于1.5m；至多孔送风顶棚孔口的水平距离不应小于0.5m。 4.在宽度小于3m的内走道顶棚上设置探测器时，宜居中布置。感温探测器的安装间距，不应超过10m；感烟探测器的安装间距，不应超过15m。探测器距端墙的距离，不应大于安装间距的一半。 5.探测器宜水平安装，当必须倾斜安装时，倾斜角度不应大于45°。 6.探测器的底座应固定牢靠，其导线连接必须可靠压接或焊接。当采用焊接时，不得使用带腐蚀性的助焊剂。 7.探测器的“+”线应为红色，“-”应为蓝色，其余线应根据不同用途采用其他颜色区分。但同一工程中相同用途的导线颜色应一致。 8.探测器底座的外接导线，应留有不小于15em的余量，入端处应有明显标志。 9.探测器底座的穿线孔宜封堵，安装完毕后的探测器底座应采取保护措施。 10.探测器的确认灯，应面向便于人员观察的主要入口方向。 11.探测器在即将调试时方可安装，在安装前应妥善保管，并应采取防尘、防潮、防腐蚀措施。

安装说明探测器可采用专用接线盒，亦可采用标准接线盒安装必要时加调整板调整安装孔距。

安装说明 1.布线要求（1）信号线Z l、Z2可选用截面≥1.0mm2的RVS型双绞铜芯线，DC24V电源线D1、D2应选用截面积≥2.5mm2的BV线。（2）本探测报警器背面有两个挂孔，可直接装在墙面的安装钉上。探测报警器须安装在使用燃气没备的房间中，安装位置应选择易发生可燃气体泄漏的位置，并尽可能面向气体扩散的方向。探测报警器的安装高度根据介质（密度大小）的不同来确定，对于轻于空气的气体（城市人工煤气、天然气），可安装在距房顶110mm的墙壁上，比空气重的气体（如液化石油气），安装高度为距地面l00mm。探测报警器安装位置与燃气没备的水平距离应在4m以内。 2.线型火灾探测器和可燃气体探测器与有特殊安装要求的探测器，应符合现行有关国家标准的规定。 Z1、Z2:与火灾报警控制器无极性信号两总线连接的端子； K l、K2：AC220V、5A常开输出控制触点端子； V1、V2：有源DC5V脉冲输出控制触点端子； A1（D1 ）、A2（D2）：电源端子，联网使用接DC24V电源，独立使用接AC220V。

火灾自动报警系统组成工作原理和适用范围

火灾自动报警系统组成工作原理和适用范围集团企业公司编码：（LL3698-KKI1269-TM2483-LUI12689-ITT289-

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火灾自动报警系统施工工艺标准

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(完整版)楼宇自控技术方案-江森自控

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在便于接线处装设接线盒。 6、金属管子入盒，盒外侧套锁母，内侧装保护口；在吊顶内敷设时，盒的内外侧均套锁母。塑料管入盒应采取相应固定措施。 7、在敷设各类管路时，采用单独的卡具固定。 8、管路的直线段每隔1.0m-1.5m设置固定点。在管路接头处、距接线盒0.2m处、管路走向改变或转角处也需设置固定点。 9、消防控制设备的外接导线，采用金属软管作套管，其长度不大于2m，且采用管卡固定，其固定点间距不大于0.5m，金属软管与消防控制设备的接线盒（箱）采用锁母固定，并根据配管规定接地。工作接地线采用铜芯绝缘导线或电缆。二、管内穿线 1、在管内或槽内穿线前，应将其内的杂物清除干净，管路清除干净后，向管内吹入少量滑石粉，以便穿线，并将管子端部装上护口，以防管口将导线绝缘

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系统（√），消防直通对讲系统（√）；四、消防控制室 1.具有消防联动功能的火灾自动报警系统的保护对象中应设置消防控制室。（√） 2.本工程消防控制室设在首层，并设有直接通往室外的出口。（√） 3.本工程消防控制室的报警控制设备由火灾报警控制主机、联动控制台、CRT显示器、打印机、应急广播设备、消防直通对讲设备、电源设备等组成。（√） 4.消防控制室可接收感烟、感温、火焰、可燃气体等探测器的火灾报警信号及水流指示器、检修间、压力报警阀、手动报警按钮、消火栓按钮的动作信号。（√） 5.消防控制室可显示消防水池、消防水箱水位，显示消防水泵的电源及运行状况。（√）； 6.消防控制室的联动控制器应能按设定的控制逻辑向各相关的受控设备发出联动控制信号，并按收相关设备的联动反馈信号。（√） 7.消防控制室的新增火灾自动报警设备应能与原有火灾自动报警设备联网及兼容，且各受控设备接口的特性参数应与消防联动控制器发出的联动控制信号相匹配。（√） 8.消防控制室应有相应的竣工图纸、各分系统控制逻辑关系说明、设备使用说明书、系统操作规程、应急预案、值班制度、维护保养制度及值班记录等文件资料。（√）