CN107913720A - A kind of V2O5‑Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst and preparation method thereof - Google Patents

A kind of V2O5‑Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst and preparation method thereof Download PDF

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CN107913720A
CN107913720A CN201610876412.0A CN201610876412A CN107913720A CN 107913720 A CN107913720 A CN 107913720A CN 201610876412 A CN201610876412 A CN 201610876412A CN 107913720 A CN107913720 A CN 107913720A
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preparation
catalyst
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scr denitration
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林啟维
胡建锋
吴晓东
石磊
陈勇
林荣贵
温明英
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Longyan Cercis Innovation Research Institute
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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Abstract

The present invention provides a kind of V2O5‑Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：Active component V2O51 5wt%；Auxiliary agent Sb2(SO4)31 5wt%；Carrier TiO290 98wt%.Present invention also offers the preparation method of denitrating catalyst, include the following steps：1)Sb2(SO4)3/TiO2The preparation of powder；2) preparation of active liquid；3) the slightly preparation of mixed pug；4) preparation of the mixed pug of essence；5) aging shaping；6) drying and calcining.Denitrating catalyst prepared by the present invention has the following advantages that：There is high activity, resistance to SO_2 is strong, recyclability is strong under low temperature.

Description

A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst and preparation method thereof
Technical field
The present invention relates to field of denitration catalyst, more particularly to a kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration is catalyzed Agent and preparation method thereof.
Background technology
Nitrogen oxides (NOx) it is NO, NO2And N2The general name of the oxynitrides such as O, sets essentially from thermal power plant, industrial thermal technology Standby and motor-vehicle tail-gas etc..NOxDepletion of the ozone layer can be caused, cause human respiratory system's disease, greenhouse effects and acid rain etc..This Outside, the NO in airxStill the arch-criminal of photochemical fog is caused.In numerous denitration technologies, NH3- SCR is because of its economy And high efficiency, become removing stationary source NOxPrevailing technology.
The V of traditional commerce2O5-WO3(MoO3)/TiO2Denitration temperature window is 300-400 DEG C, in order to avoid Repeat-heating cigarette Gas, reactor are typically mounted at before desulfurization, dedusting, the flue dust of the flue gas section high concentration can reduce catalyst denitration efficiency and Service life, and the improvement cost of equipment is big.Therefore, the highly desirable a kind of NH of low temperature high activity of exploitation of people3- SCR is urged Agent, makes reactor be arranged in after desulfurization, dedusting, so as to improve the service life of catalyst, reduces the operating cost of equipment.
Although low-temperature SCR reactor can be placed in after desulfurizer, the still SO containing low concentration in flue gas2, SO under cryogenic2The denitration activity of catalyst can be significantly reduced.First, part SO2It is converted under the action of catalyst SO3Afterwards, the NH with being sprayed into as reducing agent3, vapor generation hydrogen sulfate ammonia, hydrogen sulfate ammonia, can be catalyzed when less than 290 DEG C Agent surface aggregation and enrichment, covering activated centre inactivate SCR catalyst.Secondly, the active component of catalyst is mostly transition Metal oxide, it is easily and SO3Reaction generates the sulfate of no catalytic activity, causes the irreversible inactivation of catalyst.Therefore, The resistance to SO_2 for improving low temperature catalyst has important research significance and economic value.
After low temperature catalyst runs a period of time under the conditions of sulfur-containing smoke gas, even if with excellent resistance to SO_2, catalyst Also can because the sulphur ammonium salt of generation cover activated centre and caused by denitration activity reduce.At this time, it may be necessary to original position is carried out again to catalyst Raw processing, i.e., make the sulphur ammonium salt decomposition of covering on a catalyst, so that activity recovery, prolongs the service life by heating.In reality In the application of border, the recyclability of low temperature catalyst is an important evaluation index.
For this reason, it may be necessary to providing under a kind of low temperature has that high activity, resistance to SO_2 be strong, the denitrating catalyst of recyclability.
The content of the invention
The invention reside in provide under low temperature to have that high activity, resistance to SO_2 be strong, V of recyclability2O5-Sb2(SO4)3/ TiO2SCR denitration and preparation method thereof.
What the present invention was realized in：
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：
Active component V2O51-5wt%；
Auxiliary agent Sb2(SO4)31-5wt%；
Carrier TiO290-98wt%.
Active component V2O5It is the active material for playing major catalytic in catalyst；Auxiliary agent Sb2(SO4)3Introducing can and Active component V2O5Synergistic effect is played, on the one hand so that catalyst has catalytic activity at low temperature, on the other hand can improve and urge The resistance to SO_2 and recyclability of agent；Carrier also has certain synergistic effect.
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take the antimony lactate of 1.46-7.32 parts by weight soluble in water, add 90-98 The titanium dioxide of parts by weight, stirs and dilute sulfuric acid is added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acid<2:3；It is quiet Postpone and filter again, obtain sediment；By sediment drying to Sb2(SO4)3/TiO2Powder；
Antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acid<2:3 be that dilute sulfuric acid is excessively main in order to keep dilute sulfuric acid excessive It is to be hydrolyzed to suppress the Sb2 (SO4) 3 of reaction generation.
2) preparation of active liquid：Take monoethanol ammonium soluble in water, add the ammonium metavanadate of 1.29-6.45 parts by weight, will be molten Liquid is heated and stirred, spare as active liquid after ammonium metavanadate is completely dissolved；
It is to make ammonium metavanadate smoothly dissolve to add monoethanol ammonium and heating.Ammonium metavanadate heat resolve is V2O5, due to The solubility of ammonium metavanadate in water is very low, it is necessary to add monoethanolamine hydrotropy.
3) Sb for preparing step 1)2(SO4)3/TiO2The mix lubricant of powder and 1-2 parts by weight is uniform, wherein lubricating Agent is that mass ratio is 1:3 to 1:5 stearic acid and lactic acid；Add active liquid, the glass fibers of 4-7 parts by weight of step 2) preparation The paper paddle cotton of peacekeeping 0.5-2 parts by weight, stirs evenly, and obtains slightly mixing pug；
When mixing, it can be mixed with all machineries that can be mixed, such as can be mixed with batch mixer；Glass Fiber is reinforcing agent, and paper paddle cotton is pore creating material.
4) step 3) obtains slightly mixing pug is uniformly mixed with the binding agent of 1-3 parts by weight, the mixed pug of essence is obtained, wherein bonding Agent is that mass ratio is 1:1 to 1:3 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, using at the same time Water or ammonium hydroxide adjust pH and moisture content so that the pH of the mixed pug of essence is more than 8, moisture content 26%-30%；
The pH of pug is more than 8, be in order to ensure the alkaline environment in pug because in alkaline conditions, the flowing of pug Property and plasticity are preferable, are conducive to the shaping of catalyst of step 5)；Moisture is excessive, and step 5) is difficult to extrusion molding, and moisture is too low, urges Easily there is crack in agent.
5) aging shaping：The essence that step 4) is obtained mixes pug and carries out aging, then extrusion molding, obtains catalyst wet embryo；
The pug mixed is placed a period of time by aging refer to, and is made fully to react and be uniformly mixed between pug, is also cried old Change.
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 50 DEG C extremely from room temperature through 0.5 DEG C/h to 1 DEG C/h 70 DEG C, and it is dry 8 hours small to 16 at 50 DEG C to 70 DEG C when；Again 500 DEG C to 600 DEG C are risen to through 10 DEG C/h to 30 DEG C/h, and When being calcined 4 hours small to 8 at 500 DEG C to 600 DEG C, that is, V is made2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst.
Calcining can calcine in Muffle furnace.The calcining of the present invention will be handled first through low temperature drying, so be to ensure Catalyst is not easy to split, because there is a molding process of low temperature drying before high-temperature calcination.The catalysis prepared by invention Agent, can cut into required length according to actual needs.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, it is dilute in step 1) The concentration of sulfuric acid is 1mol/L-2mol/L.
The solubility of dilute sulfuric acid is best in this scope, antimony lactate and dilute sulfuric acid reaction effect.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, breast in step 1) Sour antimony and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:2 to 1:4.
Antimony lactate and dilute sulfuric acid molar ratio can both ensure excessive acid, keep the acid needed for reaction system in this scope Property environment, and can be to avoid the sour too many waste that cause acid.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, it is quiet in step 1) Put the time for 6 hours to 10 it is small when.
Standing is in order to enable Sb2(SO4)3/TiO2Preferably combine and precipitate.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, step 1) is middle to dry Dry condition is：At 100 DEG C -140 DEG C dry 12 hours to 36 it is small when.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, in step 2) plus Hot temperature is 60 DEG C -90 DEG C.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, ammonia in step 4) The mass concentration of water is 15% to 25%.
Ammonium hydroxide is added, is in order to adjust the mixed pug of essence to be allowed to that alkalescence is presented.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, it is old in step 5) The rotten time for 12 hours to 24 it is small when.
Aging a period of time, is in order to enable component reaction is more abundant between pug.
Preferably, the V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, step 5) is middle will Catalyst is extruded as cellular.
The invention has the advantages that：
V2O5Denitration efficiency is high, selectivity is good, and is not easy and SO3Reaction generation sulfate, so it is current business NH3The main active component of-SCR catalyst.Sb2(SO4)3In Sb elements due to Sb-O bond strengths it is weaker, NH4HSO4Salt is easy It is desorbed and decomposes from catalyst surface, therefore catalyst has good low temperature resistance to SO_2, while SO4 2-Catalysis can not only be improved The acidity of agent, is conducive to NH3Adsorbed in catalyst surface, promote SCR reactions to carry out, and SO can be suppressed2It is changed into SO3.Grind Study carefully and find SO4 2-NH can also be reduced4HSO4The decomposition temperature of salt on a catalyst, contributes to after catalyst sulfur poisoning at regeneration Reason.In short, denitration efficiency is high at the catalyst for preparing of the present invention is 175-300 DEG C in flue-gas temperature, and with excellent low Warm resistance to SO_2 and recyclability.
Brief description of the drawings
The catalyst activity of Fig. 1 difference content of vanadium；
The catalyst activity of Fig. 2 difference antimony contents.
Embodiment
In order to describe the technical content, the structural feature, the achieved object and the effect of this invention in detail, below in conjunction with embodiment And attached drawing is coordinated to be explained in detail.
Embodiment 1
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：
Active component V2O51wt%；
Auxiliary agent Sb2(SO4)31wt%；
Carrier TiO298wt%.
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take 1.46kg antimony lactates soluble in water, add 98kg titanium dioxides, stirring And 2mol/L dilute sulfuric acids are added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:2；Stand 6 it is small when after take out again Filter, obtains sediment；Sb is obtained when drying 36 is small at 100 DEG C by sediment2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, add 1.29kg ammonium metavanadates, solution is heated to 90 DEG C And stir, it is spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 1kg mix lubricants are uniform, and wherein lubricant is quality Than for 1:3 stearic acid and lactic acid；Active liquid, 4kg glass fibres and the 2kg paper paddle cottons of step 2) preparation are added, stirring is equal It is even, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 1kg binding agents, obtains the mixed pug of essence, wherein binding agent is quality Than for 1:1 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, while with water or mass concentration PH and moisture content are adjusted for 15% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 30%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 12 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 50 DEG C from room temperature through 0.5 DEG C/h, and at 50 DEG C When lower drying 16 is small；600 DEG C are risen to through 30 DEG C/h, and when calcination 4 is small at 600 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2 Low temperature SCR denitration catalyst.
Embodiment 2
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：
Active component V2O55wt%；
Auxiliary agent Sb2(SO4)35wt%；
Carrier TiO290wt%.
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take 7.32kg antimony lactates soluble in water, add 90kg titanium dioxides, stirring And 1mol/L dilute sulfuric acids are added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:3；Stand 10 it is small when after again Filter, obtain sediment；Sb is obtained when drying 12 is small at 140 DEG C by sediment2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, add 6.45kg ammonium metavanadates, solution is heated to 60 DEG C And stir, it is spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 2kg mix lubricants are uniform, and wherein lubricant is quality Than for 1:5 stearic acid and lactic acid；Add active liquid, 7kg glass fibres and the 0.5kg paper paddle cottons of step 2) preparation, stirring Uniformly, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 2kg binding agents, obtains the mixed pug of essence, wherein binding agent is quality Than for 1:3 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, while with water or mass concentration PH and moisture content are adjusted for 17% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 29%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 24 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 60 DEG C from room temperature through 0.6 DEG C/h, and at 60 DEG C When lower drying 12 is small；500 DEG C are risen to through 10 DEG C/h, and when calcination 8 is small at 500 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2 Low temperature SCR denitration catalyst.
Embodiment 3
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：
Active component V2O53wt%；
Auxiliary agent Sb2(SO4)33wt%；
Carrier TiO294wt%.
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take 4.38kg antimony lactates soluble in water, add 94kg titanium dioxides, stirring And 1.5mol/L dilute sulfuric acids are added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:4；Stand 7 it is small when after again Filter, obtain sediment；Sb is obtained when drying 18 is small at 110 DEG C by sediment2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, add 3.87kg ammonium metavanadates, solution is heated to 70 DEG C And stir, it is spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 1.2kg mix lubricants are uniform, and wherein lubricant is matter Amount is than being 1:4 stearic acid and lactic acid；Add active liquid, 5kg glass fibres and the 1kg paper paddle cottons of step 2) preparation, stirring Uniformly, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 3kg binding agents, obtains the mixed pug of essence, wherein binding agent is quality Than for 1:2 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, while with water or mass concentration PH and moisture content are adjusted for 20% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 28%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 15 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 70 DEG C from room temperature through 0.7 DEG C/h, and at 70 DEG C When lower drying 8 is small；550 DEG C are risen to through 20 DEG C/h, and when calcination 6 is small at 550 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2 Low temperature SCR denitration catalyst.
Embodiment 4
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：
Active component V2O52wt%；
Auxiliary agent Sb2(SO4)34wt%；
Carrier TiO294wt%.
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take 5.84kg antimony lactates soluble in water, add 94kg titanium dioxides, stirring And 1mol/L dilute sulfuric acids are added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:4；Stand 8 it is small when after take out again Filter, obtains sediment；Sb is obtained when drying 24 is small at 120 DEG C by sediment2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, add 2.58kg ammonium metavanadates, solution is heated to 80 DEG C And stir, it is spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 1.4kg mix lubricants are uniform, and wherein lubricant is matter Amount is than being 1:4 stearic acid and lactic acid；Active liquid, 6kg glass fibres and the 1.5kg paper paddle cottons of step 2) preparation are added, is stirred Mix uniformly, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 1.5kg binding agents, obtains the mixed pug of essence, wherein binding agent is matter Amount is than being 1:3 methylcellulose and polyoxyethylene；Slightly in mixed pug and binding agent mixed process, at the same it is dense with water or quality Spend and adjust pH and moisture content for 22% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 27%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 18 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 55 DEG C from room temperature through 0.9 DEG C/h, and at 55 DEG C When lower drying 14 is small；520 DEG C are risen to through 15 DEG C/h, and when calcination 5 is small at 520 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2 Low temperature SCR denitration catalyst.
Embodiment 5
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content are as follows：
Active component V2O51wt%；
Auxiliary agent Sb2(SO4)35wt%；
Carrier TiO294wt%.
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take 7.32kg antimony lactates soluble in water, add 94kg titanium dioxides, stirring And 2mol/L dilute sulfuric acids are added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:3；Stand 9 it is small when after take out again Filter, obtains sediment；Sb is obtained when drying 30 is small at 130 DEG C by sediment2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, add 1.29kg ammonium metavanadates, solution is heated to 75 DEG C And stir, it is spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 1.6kg mix lubricants are uniform, and wherein lubricant is matter Amount is than being 1:5 stearic acid and lactic acid；Add active liquid, 6kg glass fibres and the 1kg paper paddle cottons of step 2) preparation, stirring Uniformly, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 2.5kg binding agents, obtains the mixed pug of essence, wherein binding agent is matter Amount is than being 1:1 methylcellulose and polyoxyethylene；Slightly in mixed pug and binding agent mixed process, at the same it is dense with water or quality Spend and adjust pH and moisture content for 25% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 26%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 21 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 65 DEG C from room temperature through 1 DEG C/h, and at 65 DEG C When drying 10 is small；570 DEG C are risen to through 25 DEG C/h, and when calcination 7 is small at 570 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2It is low Warm SCR denitration.
Embodiment 6
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content such as following table：
Sequence number Active component V2O5 Auxiliary agent Sb2(SO4)3 Carrier TiO2
1 1wt% 3.5wt% 95.5wt%
2 2wt% 3.5wt% 94.5wt%
3 3wt% 3.5wt% 93.5wt%
4 4wt% 3.5wt% 92.5wt%
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：Take four parts of 5.11kg antimony lactates soluble in water, be separately added into 95.5kg, 94.5kg, 93.5kg, 92.5kg titanium dioxide, stir and 1.5mol/L dilute sulfuric acids are added dropwise into solution, antimony lactate rubs with dilute sulfuric acid You compare nAntimony lactate:nDilute sulfuric acidFor 1:4；Stand 7 it is small when after filter again, obtain sediment；When by sediment, drying 18 is small at 110 DEG C Obtain Sb2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, be separately added into 1.29kg, 2.58kg, 3.87kg, 5.16kg Ammonium metavanadate, is heated to 70 DEG C by solution and stirs, spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 1.2kg mix lubricants are uniform, and wherein lubricant is matter Amount is than being 1:4 stearic acid and lactic acid；Add active liquid, 5kg glass fibres and the 1kg paper paddle cottons of step 2) preparation, stirring Uniformly, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 3kg binding agents, obtains the mixed pug of essence, wherein binding agent is quality Than for 1:2 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, while with water or mass concentration PH and moisture content are adjusted for 20% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 28%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 15 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 70 DEG C from room temperature through 0.7 DEG C/h, and at 70 DEG C When lower drying 8 is small；550 DEG C are risen to through 20 DEG C/h, and when calcination 6 is small at 550 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2 Low temperature SCR denitration catalyst.
Obtained catalyst is cut into size and carries out active appraisal experiment for 35*35*200mm modules, and wherein flue gas condition is： NO=NH3=1000ppm, O2=5.0%, SO2=250ppm, H2O=10%, N2Balance, GHSV=5000h-1.As a result such as Fig. 1 Shown, as can be seen from the figure the catalyst of different content of vanadium all has an excellent low-temperature denitration activity, especially V3Sb3.5Ti and V4Sb3.5Ti catalyst denitration efficiency at 175-300 DEG C is higher than 80%.
Embodiment 7
A kind of V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, the denitrating catalyst each component content such as following table：
Sequence number Active component V2O5 Auxiliary agent Sb2(SO4)3 Carrier TiO2
1 3wt% 2.5wt% 94.5wt%
2 3wt% 3wt% 94wt%
3 3wt% 3.5wt% 93.5wt%
4 3wt% 4wt% 93wt%
Above-mentioned V2O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, includes the following steps：
1)Sb2(SO4)3/TiO2The preparation of powder：3.725kg, 4.38kg, 5.11kg, 5.8kg antimony lactate is taken to be dissolved in respectively In water, 94.5kg, 94kg, 93.5kg, 93kg titanium dioxide are separately added into, stirs and 1.5mol/L dilute sulfuric acids is added dropwise into solution, Antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acidFor 1:4；Stand 7 it is small when after filter again, obtain sediment；By sediment 110 Sb is obtained when drying 18 is small at DEG C2(SO4)3/TiO2Powder；
2) preparation of active liquid：Take monoethanol ammonium soluble in water, take four parts of 3.87kg ammonium metavanadates respectively, solution is heated To 70 DEG C and stir, it is spare as active liquid after ammonium metavanadate is completely dissolved；
3) Sb for preparing step 1)2(SO4)3/TiO2Powder and 1.2kg mix lubricants are uniform, and wherein lubricant is matter Amount is than being 1:4 stearic acid and lactic acid；Add active liquid, 5kg glass fibres and the 1kg paper paddle cottons of step 2) preparation, stirring Uniformly, obtain slightly mixing pug；
4) step 3) obtains slightly mixing pug is uniformly mixed with 3kg binding agents, obtains the mixed pug of essence, wherein binding agent is quality Than for 1:2 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, while with water or mass concentration PH and moisture content are adjusted for 20% ammonium hydroxide so that the pH of the mixed pug of essence is more than 8, moisture content 28%；
5) aging shaping：The essence that step 4) is obtained mix pug carry out aging 15 it is small when, then be extruded into cellular, urged Agent wet embryo；
6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 70 DEG C from room temperature through 0.7 DEG C/h, and at 70 DEG C When lower drying 8 is small；550 DEG C are risen to through 20 DEG C/h, and when calcination 6 is small at 550 DEG C, that is, V is made again2O5-Sb2(SO4)3/TiO2 Low temperature SCR denitration catalyst.
Obtained catalyst is cut into size and carries out active appraisal experiment for 35*35*200mm modules, and wherein flue gas condition is： NO=NH3=1000ppm, O2=5.0%, SO2=250ppm, H2O=10%, N2Balance, GHSV=5000h-1.As a result such as Fig. 2 Shown, as can be seen from the figure the catalyst of different antimony contents is all active with excellent low-temperature denitration, such as V3Sb3Ti, V3Sb3.5Ti and V3Sb4Ti catalyst denitration efficiency at 175-300 DEG C is higher than 80%.
Embodiment 8
It is in flue gas condition by V3Sb3.5Ti catalyst prepared by embodiment 3：NO=NH3=1000ppm, O2=5.0%, SO2=250ppm, H2O=10%, N2Balance, GHSV=5000h-1, sulphur senile experiment is carried out at T=220 DEG C, the results show is urged After agent continuously runs 48h, denitration efficiency is reduced only by 10%, shows that catalyst has excellent resistance to SO_2.
Embodiment 9
It is in flue gas condition by V3Sb3.5Ti catalyst prepared by embodiment 3：NO=NH3=1000ppm, O2=5.0%, SO2=250ppm, H2O=10%, N2Balance, GHSV=5000h-1, at T=220 DEG C after continuous operation 150h, catalyst it is de- Nitre efficiency drops to 60% from 93%, and after the catalyst of sulfur poisoning is heated 2h at 330 DEG C, the denitration efficiency of catalyst is again extensive Again to 90%, show that catalyst has excellent recyclability.
The foregoing is merely the embodiment of the present invention, not thereby limits scope of patent protection of the invention, every utilization The equivalent structure or equivalent flow shift that description of the invention and accompanying drawing content are made, it is related to be directly or indirectly used in other Technical field, be included within the scope of the present invention.

Claims (10)

  1. A kind of 1. V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst, it is characterised in that the denitrating catalyst each component contains Amount is as follows：
    Active component V2O51-5wt%；
    Auxiliary agent Sb2(SO4)31-5wt%；
    Carrier TiO290-98wt%.
  2. 2. V as claimed in claim 12O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, including it is as follows Step：
    1)Sb2(SO4)3/TiO2The preparation of powder：Take the antimony lactate of 1.46-7.32 parts by weight soluble in water, add 90-98 weight The titanium dioxide of part, stirs and dilute sulfuric acid is simultaneously added dropwise into solution, antimony lactate and dilute sulfuric acid molar ratio nAntimony lactate:nDilute sulfuric acid<2:3；After standing Filter again, obtain sediment；By sediment drying to Sb2(SO4)3/TiO2Powder；
    2) preparation of active liquid：Take monoethanol ammonium soluble in water, add the ammonium metavanadate of 1.29-6.45 parts by weight, by solution plus Heat simultaneously stirs, spare as active liquid after ammonium metavanadate is completely dissolved；
    3) Sb for preparing step 1)2(SO4)3/TiO2The mix lubricant of powder and 1-2 parts by weight is uniform, and wherein lubricant is Mass ratio is 1:3 to 1:5 stearic acid and lactic acid；Add step 2) preparation active liquid, 4-7 parts by weight glass fibre and The paper paddle cotton of 0.5-2 parts by weight, stirs evenly, and obtains slightly mixing pug；
    4) step 3) obtains slightly mixing pug is uniformly mixed with the binding agent of 1-3 parts by weight, obtains the mixed pug of essence, and wherein binding agent is Mass ratio is 1:1 to 1:3 methylcellulose and polyoxyethylene；Slightly mixed pug with binding agent mixed process, while with water or Person's ammonium hydroxide adjusts pH and moisture content so that the pH of the mixed pug of essence is more than 8, moisture content 26%-30%；
    5) aging shaping：The essence that step 4) is obtained mixes pug and carries out aging, then extrusion molding, obtains catalyst wet embryo；
    6) drying and calcining：The catalyst wet embryo that step 5) obtains is slowly increased to 50 DEG C to 70 from room temperature through 0.5 DEG C/h to 1 DEG C/h DEG C, and it is dry 8 hours small to 16 at 50 DEG C to 70 DEG C when；Again 500 DEG C to 600 DEG C are risen to through 10 DEG C/h to 30 DEG C/h, and Be calcined at 500 DEG C to 600 DEG C 4 hours to 8 it is small when, that is, be made V2O5-Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst.
  3. 3. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In the concentration of dilute sulfuric acid is 1mol/L-2mol/L in step 1).
  4. 4. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In antimony lactate and dilute sulfuric acid molar ratio n in step 1)Antimony lactate:nDilute sulfuric acidFor 1:2 to 1:4.
  5. 5. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In, in step 1) time of repose for 6 hours to 10 it is small when.
  6. 6. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In drying condition is in step 1)：At 100 DEG C -140 DEG C dry 12 hours to 36 it is small when.
  7. 7. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In heating-up temperature is 60 DEG C -90 DEG C in step 2).
  8. 8. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In the mass concentration of ammonium hydroxide is 15% to 25% in step 4).
  9. 9. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In, in step 5) the aging time for 12 hours to 24 it is small when.
  10. 10. V as claimed in claim 22O5-Sb2(SO4)3/TiO2The preparation method of low temperature SCR denitration catalyst, its feature exist In catalyst being extruded as in step 5) cellular.
CN201610876412.0A 2016-10-08 2016-10-08 A kind of V2O5‑Sb2(SO4)3/TiO2Low temperature SCR denitration catalyst and preparation method thereof Pending CN107913720A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112473689A (en) * 2020-11-23 2021-03-12 江苏新中金环保科技股份有限公司 Preparation method of nitrate type ultralow-temperature denitration granular catalyst
CN114705805A (en) * 2022-03-28 2022-07-05 承德建龙特殊钢有限公司 Method for determining vanadium pentoxide in ammonium polyvanadate and application

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EP0686423A2 (en) * 1994-06-08 1995-12-13 Mitsubishi Jukogyo Kabushiki Kaisha Ammonia decomposition catalysts
CN101862651A (en) * 2010-06-29 2010-10-20 浙江大学 V-Sb-Nb/Ti catalyst for selective catalytic reduction of nitric oxide and preparation method
CN102527371A (en) * 2010-12-14 2012-07-04 韩国科学技术研究院 SCR denitrification catalyst and the fabrication method thereof using titania hydrate slurry
CN104998680A (en) * 2015-07-13 2015-10-28 煤炭工业济南设计研究院有限公司 Low temperature denitration catalyst for anti-SO2 and H2O poisoning and preparation method of same

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Publication number Priority date Publication date Assignee Title
EP0686423A2 (en) * 1994-06-08 1995-12-13 Mitsubishi Jukogyo Kabushiki Kaisha Ammonia decomposition catalysts
CN101862651A (en) * 2010-06-29 2010-10-20 浙江大学 V-Sb-Nb/Ti catalyst for selective catalytic reduction of nitric oxide and preparation method
CN102527371A (en) * 2010-12-14 2012-07-04 韩国科学技术研究院 SCR denitrification catalyst and the fabrication method thereof using titania hydrate slurry
CN104998680A (en) * 2015-07-13 2015-10-28 煤炭工业济南设计研究院有限公司 Low temperature denitration catalyst for anti-SO2 and H2O poisoning and preparation method of same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112473689A (en) * 2020-11-23 2021-03-12 江苏新中金环保科技股份有限公司 Preparation method of nitrate type ultralow-temperature denitration granular catalyst
CN114705805A (en) * 2022-03-28 2022-07-05 承德建龙特殊钢有限公司 Method for determining vanadium pentoxide in ammonium polyvanadate and application
CN114705805B (en) * 2022-03-28 2024-01-16 承德建龙特殊钢有限公司 Determination method and application of vanadium pentoxide in ammonium polyvanadate

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