CN108187732A - A kind of CH of sulfur resistive water resistant4SCR denitration and preparation method thereof - Google Patents

A kind of CH of sulfur resistive water resistant4SCR denitration and preparation method thereof Download PDF

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CN108187732A
CN108187732A CN201711319123.1A CN201711319123A CN108187732A CN 108187732 A CN108187732 A CN 108187732A CN 201711319123 A CN201711319123 A CN 201711319123A CN 108187732 A CN108187732 A CN 108187732A
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beta
indium
scr denitration
catalyst
water resistant
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CN108187732B (en
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朱荣淑
温正中
张改革
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Shenzhen Graduate School Harbin Institute of Technology
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

The present invention provides a kind of CH of sulfur resistive water resistant4SCR denitration and preparation method thereof, active constituent are indium and Co3O4, the Co3O4It is mixed with H Beta molecular sieves, the indium is supported on by ion-exchange on H Beta molecular sieves, the Co3O4Mass ratio with H Beta is（2~20）：40, the weight percent that the indium accounts for catalyst is 2 ~ 5wt%.Technical solution using the present invention, the CH4In SCR denitration, Co3O4Play concerted catalysis with In/H Beta, still there is very high denitration performance under conditions of sulfur-bearing is aqueous.

Description

A kind of CH of sulfur resistive water resistant4SCR denitration and preparation method thereof
Technical field
The invention belongs to catalyst technical field more particularly to a kind of CH of sulfur resistive water resistant4SCR denitration and its Preparation method.
Background technology
With industry, the fast development of traffic, nitrogen oxides (NOx) pollution be on the rise.NOxIt is to lead to acid rain, photochemistry One of the main reason for a series of severe airs such as smog pollute, these pollutants all greatly endanger health and the life of the mankind Dis environment.In recent years, CH4As reducing agent selective reduction (CH4-SCR)NOxTechnology obtains the extensive concern of domestic and foreign scholars, Wherein molecular sieve carried catalyst containing In is concerned when with high denitration efficiency.Wang Xiaodong etc. finds that In/ZSM-5 can be efficient NO is restored, NO conversion ratios are up to 100%.Pan Hua etc. has found In/H-Beta catalyst in CH4- SCR system denitration rates are very high, and 450 DEG C or more when denitration rate be more than 90%.We have compareed under the same terms In/H-ZSM-5 and In/H-Beta to NOxConversion effect Rate, respectively 50% and 90%, H-Beta load In catalyst show more superior catalytic activity.But, it has been found that Under the conditions of aqueous sulfur-bearing, the catalytic denitration efficiency of In/H-Beta drops to the anti-of 30%, In/H-Beta catalyst from 90% Sulphur water-resistance is very poor.Shi Yao et al. report the Co-In/H-Beta denitrating catalysts prepared with infusion process under low-speed with etc. With certain sulfur resistive water repelling property during gas ions technology synergy.However, under the conditions of high-speed, the Co-In/ of infusion process preparation The catalytic performance of H-Beta catalytic methanes reduction NOx is still very low, to be improved.
Invention content
For more than technical problem, the invention discloses a kind of CH of sulfur resistive water resistant4SCR denitration and its preparation Method improves the water resistant resistance to SO_2 of In/H-Beta catalyst, and with good denitration rate.
In this regard, the technical solution adopted by the present invention is：
A kind of CH of sulfur resistive water resistant4SCR denitration, active constituent are indium and Co3O4, the Co3O4With H-Beta Molecular sieve mixes, and the indium is supported on by ion-exchange on H-Beta molecular sieves.Using this technical solution, the CH4-SCR Denitrating catalyst remains to have good catalytic activity under sulfur-bearing aqueous conditions, and with very high denitration rate.
As a further improvement on the present invention, the Co3O4Mixing quality ratio with H-Beta is (2~20)：40.
As a further improvement on the present invention, the weight percent that the indium accounts for catalyst is 2~5%.Further preferably , the weight percent that the indium accounts for catalyst is 2.48~4.68wt%.
As a further improvement on the present invention, the weight percent that the indium accounts for catalyst is 3.36~4.50wt%, excellent Choosing, the weight percent that the indium accounts for catalyst is 4.50%.
As a further improvement on the present invention, the Co3O4Mass ratio with H-Beta is (5~10)：40.Preferably, institute State Co3O4Mass ratio with H-Beta is 5：40.
As a further improvement on the present invention, the silica alumina ratio of the H-Beta molecular sieves is 25~40.Preferably, described point The silica alumina ratio of son sieve is 25.
As a further improvement on the present invention, the CH4SCR denitration is prepared using ion-exchange.
As a further improvement on the present invention, the CH of the sulfur resistive water resistant4SCR denitration uses following steps It is prepared：
Step S1：Prepare nitric acid solution of indium；Preferably, a concentration of 0.0066~0.066mol/L of nitric acid solution of indium；
Step S2：The nitric acid solution of indium being configured to step S1 wherein adds in H-Beta molecular screen primary powders and Co3O4, mixing is After even, constant temperature stirs 2~10h at 75~95 DEG C, then filters, and washes；Preferred washing is until the pH of lower clear liquid is 7；
Step S3：Filter cake after filtering is dried, is calcined after grinding, obtains the efficient CH4SCR denitration is catalyzed Agent, wherein, calcination temperature is 400~600 DEG C, and calcination time is 2~6h.
As a further improvement on the present invention, in step S1, a concentration of 0.01~0.033mol/ of the nitric acid solution of indium L；In step S2, constant temperature stirs 8~10h at 85 DEG C after mixing.
Preferably, a concentration of 0.033mol/L of the nitric acid solution of indium.
Preferably, in step S3, the calcination temperature is 400~500 DEG C.It is further preferred that the calcination temperature is 500℃。
The invention also discloses a kind of CH of the sulfur resistive water resistant described in as above any one4The preparation of SCR denitration Method, it is characterised in that：It includes the following steps：
Step S1：Prepare a concentration of 0.0066~0.066mol/L of nitric acid solution of indium, wherein nitric acid solution of indium；
Step S2：The nitric acid solution of indium being configured to step S1 wherein adds in H-Beta molecular screen primary powders and Co3O4, mixing is After even, constant temperature stirs 2~10h at 75~95 DEG C, then filters, and washing is until the pH of lower clear liquid is 7；
Step S3：Filter cake after filtering is dried, is calcined after grinding, obtains the efficient CH4SCR denitration is catalyzed Agent, wherein, calcination temperature is 400~600 DEG C, and calcination time is 2~6h.
As a further improvement on the present invention, in step S1, a concentration of 0.01~0.033mol/ of the nitric acid solution of indium L。
As a further improvement on the present invention, in step S2, constant temperature stirs 8~10h at 85 DEG C after mixing.
As a further improvement on the present invention, in step S3, the calcination temperature is 400~500 DEG C.Further preferably, The calcination temperature is 500 DEG C.
As a further improvement on the present invention, in step S1, a concentration of 0.033mol/L of the nitric acid solution of indium.
As a further improvement on the present invention, the Co3O4Mass ratio with H-Beta is (5~10):40.
As a further improvement on the present invention, in step S2, constant temperature stirs 8h at 85 DEG C after mixing.
As a further improvement on the present invention, in step S3, the catalyst after calcining is sieved after tabletting, grinding with sieve Point.
Our research approach shows：Existing documents and materials show NO2Generation is the key that methane activation.At us Co is found in previous work3O4Metal oxides is waited to be demonstrated by well being catalyzed the activity of NO2 generations.In this work, compare Co3O4Etc. metal oxide modifieds In-H-Beta water resistants sulfur resistive activity, the Co best to effect3O4Modified catalyst has carried out excellent Change, including preparation method, H-Beta silica alumina ratios, Co3O4The preparation conditions such as content, In carrying capacity and calcination temperature.
Compared with prior art, beneficial effects of the present invention are：
Technical solution using the present invention, the CH4In SCR denitration, Co3O4It is played with In-H-Beta molecular sieves Synergistic effect remains to have very high denitration rate under conditions of sulfur-bearing is aqueous.
Description of the drawings
Fig. 1 is the catalysis work of ionic type metal predecessor modification In-H-Beta under the conditions of 1 aqueous sulfur-bearing of comparative example of the present invention Property figure.Wherein, Fig. 1 (a) is the NO of ionic type metal predecessor modification In-H-Beta under the conditions of aqueous sulfur-bearingxPair of removal rate Than figure, Fig. 1 (b) is the CH of ionic type metal predecessor modification In-H-Beta under the conditions of aqueous sulfur-bearing4The comparison diagram of conversion ratio, Fig. 1 (c) is ionic type metal predecessor modification In-H-Beta CH under the conditions of aqueous sulfur-bearing4To NOxThe comparison diagram of selectivity.
Fig. 2 is the catalytic activity figure of metal oxide modified In-H-Beta under the conditions of 2 aqueous sulfur-bearing of the embodiment of the present invention. Wherein, Fig. 2 (a) is the NO of metal oxide modified In-H-Beta under the conditions of aqueous sulfur-bearingxThe comparison diagram of removal rate, Fig. 2 (b) CH for metal oxide modified In-H-Beta under the conditions of aqueous sulfur-bearing4The comparison diagram of conversion ratio, Fig. 2 (c) are aqueous sulfur-bearing item The CH of metal oxide modified In-H-Beta molecular sieves under part4To NOxThe comparison diagram of selectivity.
Fig. 3 is the In-Co of distinct methods preparation under the conditions of 2 aqueous sulfur-bearing of comparative example of the present invention3O4The catalysis of/H-Beta is lived Property figure.Wherein, Fig. 3 (a) is the In-Co of distinct methods preparation under the conditions of aqueous sulfur-bearing3O4The NO of/H-BetaxThe comparison of removal rate Figure, Fig. 3 (b) are the In-Co of distinct methods preparation under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4The comparison diagram of conversion ratio, Fig. 3 (c) In-Co prepared for distinct methods under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4To NOxThe comparison diagram of selectivity.
Fig. 4 is the In-Co of different silica alumina ratios under the conditions of 3 aqueous sulfur-bearing of the embodiment of the present invention3O4The catalytic activity of/H-Beta Figure.Wherein, Fig. 4 (a) is the In-Co of different silica alumina ratios under the conditions of aqueous sulfur-bearing3O4The NO of/H-BetaxThe comparison diagram of removal rate, Fig. 4 (b) is the In-Co of different silica alumina ratios under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4The comparison diagram of conversion ratio.
Fig. 5 is the In-Co of different silica alumina ratios under the conditions of the anhydrous no sulphur of the embodiment of the present invention 33O4The catalytic activity of/H-Beta Figure.Wherein, Fig. 5 (a) is the In-Co of different silica alumina ratios under the conditions of anhydrous no sulphur3O4The NO of/H-BetaxThe comparison diagram of removal rate, Fig. 5 (b) is the In-Co of different silica alumina ratios under the conditions of anhydrous no sulphur3O4The CH of/H-Beta4The comparison diagram of conversion ratio, Fig. 5 (c) are The In-Co of different silica alumina ratios under the conditions of anhydrous no sulphur3O4The CH of/H-Beta4To NOxThe comparison diagram of selectivity.
Fig. 6 is difference Co under the conditions of 4 aqueous sulfur-bearing of the embodiment of the present invention3O4The In-Co of/H-Beta mass ratioes3O4/H- The catalytic activity figure of Beta.Wherein, Fig. 6 (a) is difference Co under the conditions of aqueous sulfur-bearing3O4The In-Co of/H-Beta mass ratioes3O4/ The NO of H-BetaxThe comparison diagram of removal rate, Fig. 6 (b) are difference Co under the conditions of aqueous sulfur-bearing3O4The In- of/H-Beta mass ratioes Co3O4The CH of/H-Beta4The comparison diagram of conversion ratio, Fig. 6 (c) are difference Co under the conditions of aqueous sulfur-bearing3O4/ H-Beta mass ratioes In-Co3O4The CH of/H-Beta4To NOxThe comparison diagram of selectivity.
Fig. 7 is the In-Co of difference In concentration under the conditions of 5 aqueous sulfur-bearing of the embodiment of the present invention3O4The catalytic activity of/H-Beta Figure.Wherein, Fig. 7 (a) is the In-Co of difference In concentration under the conditions of aqueous sulfur-bearing3O4The NO of/H-BetaxThe comparison diagram of removal rate, Fig. 7 (b) is the In-Co of difference In concentration under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4The comparison diagram of conversion ratio, Fig. 7 (c) are The In-Co of difference In concentration under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4To NOxThe comparison diagram of selectivity.
Fig. 8 is the In-Co that different calcination temperatures obtain under the conditions of 6 aqueous sulfur-bearing of the embodiment of the present invention3O4/ H-Beta's urges Change activity figure.Wherein, the In-Co that Fig. 8 (a) is obtained for calcination temperatures different under the conditions of aqueous sulfur-bearing3O4The NO of/H-BetaxRemoval The comparison diagram of rate, the In-Co that Fig. 8 (b) is obtained for calcination temperatures different under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4Conversion ratio Comparison diagram, Fig. 8 (c) is the In-Co that different calcination temperatures obtain under the conditions of aqueous sulfur-bearing3O4The CH of/H-Beta4To NOxSelection The comparison diagram of property.
Specific embodiment
The preferably embodiment of the present invention is described in further detail below.
Embodiment 1
The activity rating of catalyst.
Catalyst activity is evaluated by temperature programmed surface reaction (TPSR) technology.Evaluation experimental is solid in continuous flowing It is carried out on fixed bed reaction unit.Appraisement system is mainly tested by air-path control system, catalyst reaction device system and on-line analysis System three parts form.Gas used in experiment is supplied by steel cylinder air lift.Pressure maintaining valve modulation gas pressure, flow stabilizing valve and mass flowmenter tune Variable-flow, gas pressure are 0.1MPa, and gas enters mixing tube after pressure maintaining valve flow stabilizing valve and flowmeter are adjusted and mixes, into Enter reaction tube and catalysis reaction occurs.Each component is a concentration of in reaction gas：NOxFor 400ppm, CH4For 400ppm, O2For 10%, SO2For 100ppm, vapor 5%, Ar is Balance Air.Total gas flow rate is 100mL/min, and catalyst amount is 100mg, air speed 23600h-1.The tube inner diameter 6mm used, outer diameter 10mm, material are quartz glass tube, among reaction tube Position is placed with silica wool, supports catalyst and it is made to be evenly distributed, and reaction tube is placed in fulgurite resistance furnace, temperature controller control resistance The heating rate of stove, catalytic reaction temperature are adjusted by temperature controller control resistance stove heat.Before temperature programming, make reaction gas At normal temperatures by catalyst, after adsorption reaction gas 1h, until NOxAnalyzer registration does not change substantially, shows to be catalyzed Agent is in adsorption saturation state, and then start program heats up, and 600 DEG C are risen to from 40 DEG C with the heating rate of 4 DEG C/min.Online inspection Examining system is by gas chromatograph (Shimadzu GC2014C) and NOxTwo kinds of instrument compositions of analyzer (MODEL-T200H).NO、NO2、NOx (NOx=NO+NO2) concentration is by NOxAnalysis-e/or determining.CH4And the CO and CO generated in reaction process2Concentration by being furnished with FID inspections Survey the gas chromatograph for determination of instrument.Before gas enters detecting instrument, drying device is first passed through to remove the water in gas.
The activity of catalyst in the reaction is by NOxConversion ratio weigh, i.e. η, as shown in formula (1).NOxConversion ratio Higher, catalyst activity is higher, i.e., η is bigger, represents that catalyst activity is better.CH4As the reducing agent of reaction, with NOxAccording to one Fixed proportionate relationship reaction, reactive chemistry formula are CH4+2NO+O2=CO2+N2+H2O, to a certain extent for, CH4Conversion NO can be reflectedxRemoval situation, thus, CH during observing response4Conversion situation be also necessary, CH4's Conversion ratio is represented by γ, as shown in formula (2).CH4To NOxSelectivity, i.e. NOxReact consumption CH4Amount account for CH4Occur The percentage of reaction total amount is represented by α, as shown in formula (3).
C (NO in formulax-in)——NOxInitial concentration, mL/m3；
c(NOx-out)——NOxExport concentration, mL/m3；
c(CH4-in)——CH4Initial concentration, mL/m3；
c(CH4-out)——CH4Export concentration, mL/m3。
Comparative example 1
Bimetallic ion loads altogether.
It is supported on H-Beta molecular sieves together with predecessor and In using ionic Co, carrying method uses ion exchange Method, prepares the load H-Beta molecular sieve catalysts of bimetallic containing In, and specific preparation process is as follows：
The SiO of H-Beta molecular sieves2/Al2O3=25 (Catalyst Factory, Nankai Univs).The active phase forerunner of modified H-Beta Object is indium nitrate, and adds in a certain amount of metal.Certain density In solions 100mL is first prepared, is added in into solution The molecular screen primary powder of 3g and a certain amount of ionic type metal Co salt are uniformly mixed, and are then placed on magnetic stirring apparatus, at 85 DEG C At a temperature of water bath with thermostatic control magnetic agitation 8 hours.Solution after stirring is put on a buchner funnel, is filtered with vacuum pump, washing is straight Until lower clear liquid pH=7.Filtrate is outwelled, the filter cake on filter paper is taken out and is put into baking oven, 80 DEG C are dried 12 hours.It will drying Catalyst take out and grind, be then placed in tube furnace and calcine, in air atmosphere, calcined 3 hours under certain temperature.Calcining Catalyst afterwards is sieved after tabletting, grinding with the sieve of 40~60 mesh.Catalyst granules after screening is put into sample cell It is sealed.
Meanwhile select seven kinds of transition metal element Cr, Mn, Fe, Ni, Cu, Zn and In systems of periodic table of elements period 4 As a comparison case, carrying method is same as above the standby load H-Beta of bimetallic containing In molecular sieve catalysts.
Catalytically active assessment is carried out according to the method described above to obtained the second metal-modified In-H-Beta catalyst of difference, Experimental result is as shown in Figure 1.From Fig. 1 (a) as can be seen that the load of six metal ion species of Cr, Mn, Fe, Ni, Cu and Zn can not Improve the water resistant resistance to SO_2 of In-H-Beta, denitration rate also decreases, all below 30%.In contrast, the load of Co then carries The high water resistant resistance to SO_2 of In-H-Beta, at 576 DEG C, denitration rate reaches more than 40%, and 652 DEG C of whens reach highest, are 49%.
Fig. 1 (b) is the CH of different second metal-modified In-H-Beta catalyst at different temperatures4Conversion ratio.From Fig. 1 (b) as can be seen that the load of seven metal ion species of Co, Cr, Mn, Fe, Ni, Cu and Zn all promotes CH4Conversion ratio increases, wherein Cr, Mn are the most apparent.Fig. 1 (c) shows all kinds of catalyst in high temperature section CH4To NOxSelectivity.It can be seen that from Fig. 1 (c) Under water sulphur existence condition compared with In-H-Beta, bimetallic addition reduces CH4To NOxSelectivity, wherein Co- CHs of the In-H-Beta under water sulphur existence condition4To NOxSelectivity is best.
It can be seen that the water resistant resistance to SO_2 of catalyst can be improved using ionic Co In-H-Beta catalyst modifications, It is general to the effect of In-H-Beta catalyst modifications using other ionic type metals, but Co-In-H-Beta catalyst is de- Nitre rate highest also only has 49%.
Embodiment 2
The denitration performance of metal oxide modified In-H-Beta catalyst.
With Co3O4In-H-Beta is modified, carrying method uses ion-exchange, and specific preparation process is as follows：
The SiO of H-Beta molecular sieves2/Al2O3=25 (Catalyst Factory, Nankai Univs).The active phase forerunner of modified H-Beta Object is indium nitrate, and adds in a certain amount of metal.Certain density In solions 100mL is first prepared, is added in into solution The molecular screen primary powder of 3g and a certain amount of metal mixed are uniform, are then placed on magnetic stirring apparatus, the constant temperature at a temperature of 85 DEG C Water-bath magnetic agitation 8 hours.Solution after stirring is put on a buchner funnel, is filtered with vacuum pump, washing is until lower clear liquid pH Until=7.Filtrate is outwelled, the filter cake on filter paper is taken out and is put into baking oven, 80 DEG C are dried 12 hours.The catalyst of drying is taken Go out and grind, be then placed in tube furnace and calcine, in air atmosphere, calcined 3 hours under certain temperature.Catalyst after calcining After tabletting, grinding, sieved with the sieve of 40~60 mesh.Catalyst granules after screening is put into sample cell and is sealed.
Meanwhile select Cr2O3、MnO2、Fe2O3, the metal oxides such as NiO, CuO, ZnO carry out as right In-H-Beta As usual, carrying method is same as above.
Catalytic activity is carried out according to the method described above to obtained difference the second metal oxide In-H-Beta catalyst to comment Valency, experimental result are as shown in Figure 2.From Fig. 2 (a) as can be seen that in seven kinds of catalyst, In-ZnO/H-Beta and In-CuO/H- Beta catalyst complete deactivations under water sulphur existence condition, but remaining five kinds of catalyst all has certain water resistant resistance to SO_2. Wherein In-Co3O4The catalytic effect of/H-Beta is best.In-Co3O4- H-Beta highest denitration rates can reach 83%.In- NiO/H-Beta、In-Fe2O3/H-Beta、In-MnO2/ H-Beta and In-Cr2O3/ H-Beta also has compared with In-H-Beta Better water resistant resistance to SO_2, highest denitration rate is respectively 72%, 70%, 64%, 44%.
Fig. 2 (b) is the CH of catalyst at different temperatures4Conversion ratio.From Fig. 2 (b) as can be seen that Co, Cr, Mn, Fe, The load of seven metal ion species of Ni, Cu and Zn all promotes CH4Conversion ratio increases.Fig. 2 (c) illustrates the CH of all kinds of catalyst4It is right NOxSelectivity.In-ZnO/H-Beta and In-CuO/H-Beta does not have denitration performance, CH under water sulphur existence4All with O2 It reacts.In remaining catalyst, In-Cr2O3The CH of/H-Beta4Conversion ratio is in high temperature section highest, CH4Selectivity is minimum, Cr2O3Presence may promote CH4It is reacted with oxygen, affects CH4Selectivity.In-Fe2O3/H-Beta、In-Co3O4/H- The CH of Beta, In-NiO/H-Beta and In-Mn/H-Beta4Conversion ratio is not much different, CH4Selectivity compared with In-H-Beta It is slightly poor, but the CH of these four catalyst4Selectivity is very stable in high temperature section, at 652 DEG C, participates in the CH of reaction4In have 40% Left and right is and NOxIt is reacted.
It can be seen that In-ZnO/H-Beta and In-CuO/H-Beta does not have denitration performance under water sulphur existence, And Cr2O3、MnO2、Fe2O3、Co3O4, NiO doping improve the sulfur resistive water-resistance of In/H-Beta, wherein In-Co3O4/H- Catalytic effects of the Beta under the conditions of water sulphur is best.
Embodiment 2 and comparative example 1 are compared, Co3O4The highest denitration rate of doping vario-property In/H-Beta up to 83%, CH4Selectivity reachable 57%, and Co3+The highest denitration rate of doping vario-property In/H-Beta is only 49%, CH4Selectivity also only has 44%.It can be seen that with Co3O4Doping vario-property is better than with Co3+Doping vario-property.
Comparative example 2
A kind of CH of sulfur resistive water resistant4SCR denitration in the present embodiment, is prepared respectively using different preparation methods In-Co3O4/ H-Beta is prepared for In-Co respectively using ion-exchange and infusion process3O4/H-Beta.The step of ion-exchange Suddenly with embodiment 2.The step of infusion process, is as follows：
With H-Beta molecular sieves (SiO2/Al2O3=25, Catalyst Factory, Nankai Univ) it is carrier, indium nitrate is predecessor, And add in Co3O4.The indium nitrate of certain mass is weighed first, is dissolved in appropriate amount of deionized water jointly, and the dosage of deionized water is with quilt Subject to the H-Beta molecular sieves and cobaltosic oxide of aimed quality just all adsorb.The nitrate solution of different activities component stirs After mixing uniformly, suitable H-Beta molecular sieves and cobaltosic oxide are added in, be mixed one hour, then aging 24 at room temperature Hour.It is dried 12 hours with 80 DEG C in an oven, then catalyst taking-up is ground, then again under air atmosphere with 500 DEG C calcining 3 hours.Finally catalyst is sieved to obtain the fine particle of 40~60 mesh.Catalyst granules obtained is put into It is sealed in sample cell.
Remaining of two different preparation methods tests preparation condition：H-Beta molecular sieves silica alumina ratio is 25, Co3O4/ H-Beta mass ratioes are 1:4, a concentration of 0.033M of ion exchange liquid, calcination temperature are 500 DEG C.In contents and ion in maceration extract The In load capacity that exchange process is prepared into catalyst is consistent.The In load capacity of catalyst is measured by ICP experiments.Two methods The In load capacity arrived the results are shown in Table 1, ion-exchange prepare In-Co3O4The mass fraction of In is in/H-Beta 3.38%.In-Co prepared by infusion process3O4The mass fraction of In is 3.55% in/H-Beta.
To the CH of the two4SCR denitration performance is tested.The catalyst prepared to ion-exchange is named as In- Co3O4/ H-Beta-E, dipping rule are named as In-Co3O4/H-Beta-I.Experimental result is as shown in Figure 3.It can from Fig. 3 Go out, infusion process prepares In-Co3O4The denitration rate of/H-Beta-I is only up to 36%, and ion-exchange prepares In-Co3O4/H- The catalytic effect of Beta-E is substantially better than infusion process.In addition, methane is to NOxSelectivity have it is significantly different.It can be seen that with Infusion process is compared, In-Co prepared by ion-exchange3O4/ H-Beta has higher CH4SCR denitration activity.
In-Co prepared by the different preparation methods of table 13O4In load capacity on/H-Beta
Embodiment 3
On the basis of the ion-exchange of comparative example 2, and silica alumina ratio is used to be sieved for 25,40,60 H-Beta molecules In-Co is not prepared for it3O4/ H-Beta, remaining experiment preparation condition：Co3O4/ H-Beta is 1:4, calcination temperature is 500 DEG C, from Son exchanges a concentration of 0.033M of liquid indium nitrate.And the CH to catalyst under sulfur-bearing aqueous conditions4SCR denitration performance carries out real It tests.The catalyst prepared to different silica alumina ratios is named as In-Co3O4/ H-Beta-x, x are silica alumina ratio；Such as In-Co3O4/H- Beta-25 shows that the silica alumina ratio of molecular sieve in catalyst is 25.Experimental result is as shown in Figure 4.
As shown in figure 4, under water sulphur existence condition, In-Co3O4/ H-Beta-40 and In-Co3O4/ H-Beta-60 is almost There is no denitration performance, but methane is still aoxidized.For this phenomenon, we supplement the catalyst under no sulphur anhydrous condition Denitration performance is tested, and experimental result is as shown in Figure 5.From figure 5 it can be seen that In-Co3O4/ H-Beta-25 denitrations at 524 DEG C Rate reaches 90.8%, In-Co3O4/ H-Beta-40 denitration rates at 524 DEG C are up to 34.4%, In-Co3O4/H-Beta- 60 do not have denitration performance.It can be seen that high silica alumina ratio is unfavorable for In-Co3O4/ H-Beta the selective catalytic denitrification process.
Embodiment 4
On the basis of the ion-exchange of comparative example 2, using different Co3O4/ H-Beta mass ratioes are prepared for In- respectively Co3O4/ H-Beta, mass ratio are respectively：Co3O4/ H-Beta=2:40、5:40、10:40、20:40、40:40、40:0, and it is right The CH of catalyst4SCR denitration performance is tested.To different Co3O4Catalyst prepared by doping is named as In-Co3O4/H- Beta(y).Y is Co3O4The ratio of/H-Beta.Experimental result is as shown in Figure 6.
By Fig. 6 (a) experimental results it is found that In-Co3O4/H-Beta(2:40) denitration performance is more general, and denitration rate is not More than 60%.In-Co3O4/H-Beta(5:40) catalytic effect is optimal, and denitration rate reaches as high as 88%.With Co3O4/H- Beta mass continues to increase than ratio, and situation about continuously decreasing occurs in the catalytic effect activity of catalyst.In-Co3O4/H-Beta (10:40) highest denitration rate is 83%, In-Co3O4/H-Beta(20:40) highest denitration rate is 76.2%, In-Co3O4/ H-Beta(40:40) highest denitration rate only has 34%.In-Co3O4/H-Beta(40:0) no H-Beta is indicated, at this time catalyst Without denitration performance, show independent Co3O4Without catalytic effect, Co3O4Play a part of co-catalyst in the catalyst.
In addition, Fig. 6 (b) and Fig. 6 (c) then represent catalyst methane conversion and methane to the selectivity of nitrogen oxides. With Co3O4/ H-Beta mass constantly reduces therewith than the methane conversion of the raising catalyst of ratio.And methane is to nitrogen oxidation Object selectivity is then in Co3O4/ H-Beta mass is 5 than ratio:Total optimization when 40.In conclusion catalyst Co3O4/H- The Co of Beta3O4/ H-Beta most ratios of greater inequality are 5:40.
Embodiment 5
On the basis of the ion-exchange of comparative example 2, it is prepared for difference respectively using different In concentration ion exchange liquids The In-Co of In load capacity3O4/ H-Beta, the In concentration is respectively 0.0066M, 0.01M, 0.033M, 0.066M.To different In The CH of the catalyst of concentration4SCR denitration performance is tested.Different ions are exchanged with catalyst prepared by liquid concentration to be named as In-Co3O4/ H-Beta-z, wherein, z is the concentration of In in ion exchange liquid, and experimental result is as shown in Figure 7.Further it has been ICP The In contents of each catalyst are surveyed in experiment, and experimental result is as shown in table 2.
In-Co prepared by 2 difference In concentration of table3O4The In load capacity of/H-Beta
It can be seen that from Fig. 7 experimental results with the increase of ion exchange liquid concentration, the denitration performance activity of catalyst is first It is reduced after raising.In-Co3O4The denitration efficiency highest of/H-Beta-0.033.And ion exchange liquid concentration is further increased, In- Co3O4/ H-Beta-0.066 highest denitrations rate is 86%.And methane conversion is not much different in figure, but methane selectively Significantly increase, and In-Co with the increase of In concentration3O4/ H-Beta-0.033 is optimal.In addition, when ion exchange liquid concentration During for 0.033M, the load capacity of In tends to saturation in catalyst.So when ion exchange liquid concentration, that is, In concentration is in 0.033M, The catalytic performance of catalyst is optimal.
Embodiment 6
On the basis of the ion-exchange of comparative example 2, the experiment of the present embodiment is using different 400 DEG C of calcination temperatures, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C be prepared for In-Co respectively3O4/ H-Beta, and to the CH of catalyst4SCR denitration performance carries out Detection.The catalyst prepared to different calcination temperatures is named as In-Co3O4/ H-Beta-a, wherein a be calcination temperature, such as In- Co3O4/ H-Beta-400 represents the catalyst that calcination temperature is 400 DEG C of preparations.Experimental result is as shown in Figure 8.
As can see from Figure 8, as calcination temperature increases, the CH of catalyst4SCR denitration activity is first increased and is reduced afterwards. Calcination temperature has best CH for the when catalyst of 500 DEG C of calcinings out4SCR denitration activity.
By above-mentioned experiment as it can be seen that ion-exchange is used to prepare, molecular sieve H-Beta silica alumina ratios is 25, In ion exchanges Liquid a concentration of 0.033M, Co3O4/ H-Beta is 5:40th, when calcination temperature is 500 DEG C, the In-Co of gained is calcined3O4/H-Beta Catalytic effect is best, and denitration rate can reach 88%.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, it is impossible to assert The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist Under the premise of not departing from present inventive concept, several simple deduction or replace can also be made, should all be considered as belonging to the present invention's Protection domain.

Claims (10)

1. a kind of CH of sulfur resistive water resistant4SCR denitration, it is characterised in that：Its active constituent is indium and Co3O4, it is described Co3O4It is mixed with H-Beta molecular sieves, the indium is supported on by ion-exchange on H-Beta molecular sieves.
2. the CH of sulfur resistive water resistant according to claim 14SCR denitration, it is characterised in that：The Co3O4With H- The mixing quality ratio of Beta is（2~20）：40.
3. the CH of sulfur resistive water resistant according to claim 14SCR denitration, it is characterised in that：The indium accounts for catalyst Weight percent be 2 ~ 5wt%.
4. the CH of sulfur resistive water resistant according to claim 14SCR denitration, it is characterised in that：The H-Beta molecules The silica alumina ratio of sieve is 25 ~ 40.
5. the CH of the sulfur resistive water resistant according to claim 1 ~ 4 any one4SCR denitration, it is characterised in that：It is adopted It is prepared with following steps：
Step S1：Prepare nitric acid solution of indium；
Step S2：The nitric acid solution of indium being configured to step S1 wherein adds in H-Beta molecular screen primary powders and Co3O4, after mixing, Constant temperature stirs 2 ~ 10h at 75 ~ 95 DEG C, then filters, and washing is until the pH of lower clear liquid is 7；
Step S3：Filter cake after filtering is dried, is calcined after grinding, obtains the efficient CH4SCR denitration, In, calcination temperature is 400 ~ 600 DEG C, and calcination time is 2 ~ 6h.
6. the CH of sulfur resistive water resistant according to claim 54SCR denitration, it is characterised in that：It is described in step S1 A concentration of 0.0066 ~ 0.066 mol/L of nitric acid solution of indium；In step S2, constant temperature stirs 8h at 85 DEG C after mixing；Step In rapid S3, the calcination temperature is 500 DEG C.
7. a kind of CH of sulfur resistive water resistant as described in claim 1 ~ 4 any one4The preparation method of SCR denitration, It is characterized in that：It includes the following steps：
Step S1：Prepare nitric acid solution of indium；
Step S2：The nitric acid solution of indium being configured to step S1 wherein adds in H-Beta molecular screen primary powders and Co3O4, after mixing, Constant temperature stirs 2 ~ 10h at 75 ~ 95 DEG C, then filters, and washes；
Step S3：Filter cake after filtering is dried, is calcined after grinding, obtains the efficient CH4SCR denitration, In, calcination temperature is 400 ~ 600 DEG C, and calcination time is 2 ~ 6h.
8. the CH of sulfur resistive water resistant according to claim 74The preparation method of SCR denitration, it is characterised in that：
In step S1, a concentration of 0.0066 ~ 0.066mol/L of nitric acid solution of indium.
9. the CH of sulfur resistive water resistant according to claim 74The preparation method of SCR denitration, it is characterised in that：
In step S1, a concentration of 0.033mol/L of the nitric acid solution of indium；In step S2, the constant temperature at 85 DEG C after mixing Stir 8h；In step S3, the calcination temperature is 500 DEG C.
10. the CH of sulfur resistive water resistant according to claim 74The preparation method of SCR denitration, it is characterised in that：Step In rapid S2, the Co3O4Mass ratio with H-Beta is (2 ~ 20):40；The silica alumina ratio of the H-Beta molecular sieves is 25 ~ 40； The weight percent that the indium accounts for catalyst is 2 ~ 5wt%.
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