CN102806102B - Catalyst for catalyzing isocyanic acid produced in urea pyrolysis process to hydrolyze so as to generate ammonia and preparation method thereof - Google Patents
Catalyst for catalyzing isocyanic acid produced in urea pyrolysis process to hydrolyze so as to generate ammonia and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for catalyzing isocyanic acid produced in a urea pyrolysis process to hydrolyze so as to generate ammonia and a preparation method of the catalyst. The catalyst is composed of a carrier, and an active component host and a doping component adjuvant which are loaded on the carrier. The carrier is a ZSM-5 molecular sieve, the active component host is titanium dioxide, and the doping component adjuvant is iron, platinum, or a mixture of iron and platinum. The catalyst provided by the invention is larger in specific surface area, more stable in performance at high temperature and higher in catalytic activity.
Description
Technical field
The present invention relates to air pollution control technique field, be specifically related to the Catalysts and its preparation method of the isocyanic acid hydrolysis ammonification producing in a kind of catalyzing urea pyrolytic process.
Background technology
At present, the reducing agent that flue gas denitrification system is conventional has ammonia, liquefied ammonia and urea, and these reducing agents, for gas denitrifying technology, can be obtained similar denitration effect.Urea is nontoxic, harmless, without explosion potential, and be convenient to transportation and store, based on the consideration of above-mentioned safety factor aspect, as reducing agent, obtained application more widely in recent years.In SCR (SCR) denitrating system, urea generally can not directly spray in catalytic reactor, but need to outside reactor, configure separately ammonia preparation system from urea.
Urea ammonia processed comprises Hydrolyze method and pyrolysismethod, and the conventional Hydrolyze method of engineering mainly contains U2A and Ammogen patented technology at present, requires pressure 1.4-2.5MPa, temperature 150-200 ℃, ammonia response time 3～5min processed; The patent No. is that 201120039713.0 Chinese utility model patent discloses a kind of urea hydrolysis ammonia producing system, comprises the urea liquid configuration-system, urea liquid stocking system and the urea liquid hydrolysising reacting system that connect successively.
Pyrolysismethod mainly contains ULTRA patented technology, requires temperature 450-600 ℃, normal pressure, ammonia response time 5～30s processed.Compare, pyrolysismethod has advantages of that ammonia response processed is fast very outstanding, can better adapt to working conditions change in actual denitrification process.
The patent No. is that 200710092607.7 Chinese invention patents disclose a kind of technique for preparing ammonia from urea by pyrolysis method, comprises the following steps: step 1, arranges urea granules and store and dissolution system; Step 2, arranges urea liquid stocking system; Step 3, arranges urea pyrolysis system; Step 4, arranges waste liquid disposal system; Step 5, is communicated with all systems in whole technique; Step 6, the storage of urea granules and dissolving; Step 7, urea decomposition produces ammonia; Step 8, liquid waste processing; The present invention's ammonia cost processed is low; Simple to operate, without high pressure, normal pressure; Response time is fast, starts reaction in 5～30 seconds; Mode of heating variation, can adopt gaseous fuel or diesel oil etc.
Urea pyrolysis ammonia end-product processed is the ammonia (NH that waits amount of substance
3) and isocyanic acid (HNCO).Although hydrolysis can further occur HNCO, generate NH
3but HNCO is highly stable under gas phase, hydrolysis only just can carry out under specific metal or metal oxide.In addition, HNCO can carry out reduction reaction with NO and generates harmful nitrous oxide (N
2o), this is disadvantageous to denitrification process.
At present, for HCNO hydrolyzing N H
3, developed corresponding catalyst, this catalyst is mainly by anatase titanium dioxide TiO
2form, still, this catalyst specific surface is less, and has high temperature deactivation phenomenon (highly active Detitanium-ore-type TiO
2crystal transition turns to low activity rutile TiO
2).
Summary of the invention
The Catalysts and its preparation method that the invention provides the isocyanic acid hydrolysis ammonia processed producing in a kind of catalyzing urea pyrolytic process, specific surface area of catalyst of the present invention is large, and at high temperature stable performance has higher catalytic activity.
The catalyst of the isocyanic acid hydrolysis ammonification producing in a kind of catalyzing urea pyrolytic process, by carrier and the active component host and the doping component auxiliary agent that load on carrier, formed, described carrier is ZSM-5 molecular sieve, described active component host is titanium dioxide, and described doping component auxiliary agent is the mixture of iron, platinum or iron and platinum.
The present invention adopts anatase type TiO
2as host, the acidic site on surface contains the hydrolysis that Lewis acid is conducive to HNCO, therefore the hydrolysis of HNCO is shown to very high activity.
Catalyst carrier is ZSM-5 molecular sieve, and surface has certain Lewis acid, is conducive to the hydrolysis of HNCO; Carrier has very large specific area simultaneously, is conducive to the absorption of isocyanic acid HCNO, is conducive to catalytic reaction.
Fe, Pt are as the auxiliary agent of catalyst, and appropriate Fe is doped to γ-Fe
2o
3form, the γ-Fe in catalyst
2o
3tiO after making to adulterate
2there is less crystallite dimension, larger specific area, suppress anatase and change to Rutile Type, thereby can make TiO
2there is higher catalytic activity; The electron distributions of appropriate Pt doping in can change system, affect surface nature, and then the catalytic activity of improvement to HNCO.
Preferably, Fe: Pt: TiO in described catalyst
2: the weight ratio of ZSM-5 molecular sieve is 0～1: 0～0.01: 2～5: 100, and Fe, Pt the two be zero when different.
Host TiO
2weight ratio continues to increase not obvious to the active recruitment of catalyst.Add a certain amount of catalyst promoter Fe, Pt and all can make the activity of catalyst increase, the active recruitment of Fe weight ratio increase examination catalyst is little, and continuing to rise to cause catalytic activity to decline; When Pt weight ratio continues to increase, the active recruitment of catalyst is little, considers the preferred aforementioned proportion of its economy.
As described in the preparation method of catalyst, comprising:
(1) dry ZSM-5 molecular sieve rear rapid stirring is dispersed in deionized water and obtains dispersion liquid, by TiO
2precursor liquid A is added drop-wise in described dispersion liquid, after hydrolysis, filters, and washing and precipitating is neutral to pH value, described precipitation roasting is obtained to the molecular sieve of load host;
Or by TiO
2precursor liquid B adjust pH to 4～5, add dried ZSM-5 molecular sieve, after dipping 30～45min, lift, and roasting obtains the molecular sieve of load host;
(2) molecular sieve of described load host is impregnated in the mixing precursor liquid of Fe precursor liquid, Pt precursor liquid or Fe and Pt, floods 12～16 hours, dry roasting, reduces in oxygen-free environment, cooling described catalyst.
Described TiO
2precursor liquid A is TiCl
4solution or Ti (SO
4)
2solution, most preferably is TiCl
4solution, TiCl
4solution loads on carrier ZSM-5 molecular sieve in hydrolytic process.
Described TiO
2precursor liquid B is Ti (OC
4h
9)
4solution or Ti (OC
3h
7)
4solution, most preferably is Ti (OC
4h
9)
4solution, Ti (OC
4h
9)
4at dipping, lift in process and load on carrier ZSM-5 molecular sieve.
TiO
2precursor liquid A reaction principle:
Hydrolysis: TiCl
4+ H
2o → TiOH
3++ H
++ 4Cl
-;
Ionization: TiOH
3+→ TiO
2++ H
+;
Hydrolysis: TiO
2++ 2H
2o → TiO
2+ 2H
+
TiO
2precursor liquid B reaction principle:
Hydrolysis: Ti (OR)
4+ 2H
2o → Ti (OH)
4+ 4ROH;
Polycondensation: Ti (OH)
4→ TiO
2+ 2H
2o
In formula, R is-C
3h
7or-C
4h
9.
Dynamic control pH value while being hydrolyzed described in step (1) is 1～3, and rapid stirring under this pH value condition, prevents TiCl
4contact water is hydrolyzed at once later, TiCl
4after hydrolysis, can load on uniformly on ZSM-5 molecular sieve.
Described in step (1), the time of hydrolysis is 45～60min.
Temperature while being hydrolyzed described in step (1) is 70～80 ℃, and temperature is too low, easily reunites; Temperature is too high, is not easy to load on carrier, so the present invention is preferably 70～80 ℃.
Roasting in step (2) is for to be fired to 300～400 ℃ in Muffle furnace, and then insulation 5min is cooled to room temperature and obtains the molecular sieve of load host; Roasting in step (3) is 300～450 ℃ of roasting 2h in Muffle furnace, is reduced to 300～400 ℃ and reduces in hydrogen, is then cooled to the molecular sieve (being catalyst) that room temperature obtains load host-auxiliary agent.
The present invention also provides a kind of method of utilizing the isocyanic acid hydrolysis ammonia processed producing in described catalyst urea pyrolysis process, and by described catalyst arrangement, in the fluid bed of urea pyrolysis system, GHSV is 4500～5500h
-1, the temperature of urea pyrolysis system is 140～400 ℃.
Preferably, the temperature of urea pyrolysis system is 220～320 ℃.
Beneficial effect of the present invention:
The present invention adopts anatase type TiO
2as host, the acidic site on surface contains the hydrolysis that Lewis acid is conducive to HNCO, therefore the hydrolysis of HNCO is shown to very high activity; Employing ZSM-5 molecular sieve is catalyst carrier, and ZSM-5 molecular sieve surface has certain Lewis acid, is conducive to the hydrolysis of HNCO, and carrier has very large specific area simultaneously, is conducive to the absorption of isocyanic acid HCNO, is conducive to catalytic reaction; Adopt Fe, the Pt auxiliary agent as catalyst, appropriate Fe is doped to γ-Fe
2o
3form, the γ-Fe in catalyst
2o
3tiO after making to adulterate
2there is less crystallite dimension, larger specific area, suppress anatase and change to Rutile Type, thereby can make TiO
2there is higher catalytic activity; The electron distributions of appropriate Pt doping in can change system, affect surface nature, and then the catalytic activity of improvement to HNCO.Catalyst of the present invention has good catalytic activity at lower temperature, improves urea and produces ammonia rate, saves cost.
Accompanying drawing explanation
Fig. 1 is urea pyrolysis ammonia system structure chart processed.
The specific embodiment
Urea pyrolysis ammonia system structure chart processed as shown in Figure 1, comprise urea granules conservation tank 1, urea screw(-type) feeder 2, urea dissolving tank 3, urea liquid delivery pump 4, urea liquid storage tank 5, air blast 7, pyrolysis tower 8, air-introduced machine 9 and urea liquid spray nozzle 10, urea granules is sent in urea dissolving tank 3 by urea screw(-type) feeder 2, from the water delivery port 6 that desalts of urea dissolving tank 3, send into the water that desalts, dissolved urea solution transfer pump 4 is sent in urea liquid storage tank 5, urea liquid atomization sprays in pyrolysis tower 8, in catalyst arrangement pyrolysis tower 8 of the present invention, pyrolysis tower 8 adopts fluid bed, bottom is bringing-up section, top is pyrolysis section, pyrolysis temperature in straying quatity and the pyrolysis tower 8 of control urea liquid.
Embodiment 1:Fe/TiO
2/ ZSM-5 catalyst (catalyst A)
In preparation 50g catalyst A, by ZSM-5 molecular sieve (Shandong Qilu Huaxin High-technology Co., Ltd. provides) in vacuum drying chamber 60 ℃ vacuumize dry 4 hours, be cooled to room temperature, standby; By pure 1ml titanium tetrachloride solution (host TiO
2presoma) be added dropwise in 450ml dispersion liquid (disperseing 48.5g ZSM-5 molecular sieve in 450ml deionized water), 70 ℃ of stirring in water bath, hydrolysis time is 45min, controlling pH is 1.0, after dropping finishes, filter, and repeatedly use deionized water rinsing, until pH value is 7.0 left and right, subsequently the molecular sieve of load host is put into Muffle furnace and be fired to 300 ℃, be incubated 5 minutes, be cooled to room temperature, standby; By equi-volume impregnating, the molecular sieve of load host is immersed under room temperature condition to 50ml iron nitrate solution (Fe presoma, iron content is 0.5g) in 12 hours, in vacuum drying chamber, 60 ℃ vacuumize dry 4 hours, 300 ℃ of roastings 2 hours in Muffle furnace again, finally 300 ℃ of reductase 12s hour in hydrogen, be cooled to room temperature, obtain Fe/TiO
2/ ZSM-5 molecular sieve (catalyst A), wherein, detects auxiliary agent Fe: host TiO by X-ray photoelectron spectroscopic analysis method
2: carrier ZSM-5=1: 2: 100 (weight ratio).
Pressing shown in Fig. 1, is 22.2m by volume
3(bulk density is 0.66g/ml) catalyst A is arranged in fluid bed, atomize urea solution concentration 50%, and flow is 5m
3/ h, heating carrier gas air air quantity is 100000Nm
3/ h, reaction temperature is at 320 ℃, GHSV (gas space velocity per hour)=4500h
-1, producing ammonia rate is 90.2%.
Produce ammonia rate computing formula as follows:
Embodiment 2:Pt/TiO
2/ ZSM-5 catalyst (catalyst B)
In preparation 50g catalyst B, ZSM-5 molecular sieve (Shandong Qilu Huaxin High-technology Co., Ltd. provides) is dried to 8 hours in 100 ℃ of thermostatic drying chambers, be cooled to room temperature, standby; By 1.5ml, be pure titanium tetrachloride solution (host TiO
2presoma) be added dropwise in 450ml dispersion liquid (450ml deionized water is disperseed 48.5g ZSM-5 molecular sieve), 80 ℃ of stirring in water bath, hydrolysis time is 60min, controlling pH is 3.0, after dropping finishes, filter, and repeatedly use deionized water rinsing, until pH value is 7.0 left and right, subsequently the molecular sieve of load host is put into Muffle furnace and be fired to 450 ℃, be incubated 5 minutes, be cooled to room temperature, standby; By equi-volume impregnating, the molecular sieve of load host is immersed under room temperature condition to 50ml platinum acid chloride solution (Pt presoma, platiniferous 0.005g) in 16 hours, dry 8 hours of 100 ℃ of thermostatic drying chambers, 450 ℃ of roastings 2 hours in Muffle furnace again, finally 400 ℃ of reductase 12s hour in hydrogen, be cooled to room temperature, obtain Pt/TiO
2/ ZSM-5 molecular sieve (catalyst B), wherein, detects auxiliary agent Pt: host TiO by X-ray photoelectron spectroscopic analysis method
2: carrier ZSM-5=0.01: 3: 100 (weight ratio).
Pressing shown in Fig. 1, is 20m by volume
3(bulk density is 0.66g/ml) catalyst B is arranged in fluid bed, atomize urea solution concentration 40%, and flow is 5m
3/ h, heating carrier gas air air quantity is 100000Nm
3/ h, reaction temperature is at 280 ℃, GHSV (gas space velocity per hour)=5000h
-1, producing ammonia rate is 91.1%.
Embodiment 3:Fe-Pt/TiO
2/ ZSM-5 catalyst (catalyst C)
In preparation 50g catalyst C, by ZSM-5 molecular sieve (Shandong Qilu Huaxin High-technology Co., Ltd. provides) in vacuum drying chamber 70 ℃ vacuumize dry 4 hours, be cooled to room temperature, standby; Ti (OC
4h
9)
4load, by 10.625gTi (OC
4h
9)
4be dissolved in ethanol, add while stirring after acetic acid, add the ethanol that contains deionized water to stir, splashing into nitric acid, to make pH value be 4, and 48.5g molecular sieve be impregnated in the colloidal sol obtaining and lifted after 30min.Subsequently the molecular sieve of load host is put into Muffle furnace and be fired to 400 ℃, be incubated 5 minutes, be cooled to room temperature, standby; Press equi-volume impregnating by the molecular sieve of load host step impregnation method by volume under room temperature condition, be immersed in 50ml ferric nitrate (Fe presoma, iron content 0.5g) and platinum acid chloride solution (Pt presoma, platiniferous 0.005g) mixed solution in 12 hours, in vacuum drying chamber, 70 ℃ vacuumize dry 4 hours, then 400 ℃ of roastings 2 hours in Muffle furnace, finally 350 ℃ of reductase 12s hour in hydrogen, be cooled to room temperature, obtain Pt/TiO
2/ ZSM-5 molecular sieve (catalyst C), wherein, detects auxiliary agent Fe by X-ray photoelectron spectroscopic analysis method: auxiliary agent Pt: host TiO
2: carrier ZSM-5=1: 0.01: 5: 100 (weight ratio).
Pressing shown in Fig. 1, is 18.2m by volume
3(bulk density is 0.66g/ml) catalyst B is arranged in fluid bed, atomize urea solution concentration 40%, and flow is 5m
3/ h, heating carrier gas air air quantity is 100000Nm
3/ h, reaction temperature is at 220 ℃, GHSV (gas space velocity per hour)=5500h
-1, producing ammonia rate is 93.7%.
Embodiment 4:Fe-Pt/TiO
2/ ZSM-5 catalyst (catalyst D)
In preparation 50g catalyst D, ZSM-5 molecular sieve (Shandong Qilu Huaxin High-technology Co., Ltd. provides) is dried to 8 hours in 110 ℃ of thermostatic drying chambers, be cooled to room temperature, standby; Ti (OC
4h
9)
4load, by 8.5gTi (OC
4h
9)
4be dissolved in ethanol, add while stirring after acetic acid, add the ethanol that contains deionized water to stir, splashing into nitric acid, to make pH value be 5,48.5g molecular sieve be impregnated in the colloidal sol obtaining and lifted after 45min, subsequently the molecular sieve of load host is put into Muffle furnace and be fired to 380 ℃, be incubated 5 minutes, be cooled to room temperature, standby; Press equi-volume impregnating by the molecular sieve of load host step impregnation method by volume under room temperature condition, be immersed in, be immersed in 50ml ferric nitrate (Fe presoma, iron content 0.25g) and the mixed solution of platinum acid chloride solution (Pt presoma, platiniferous 0.0025g) in 16 hours, dry 8 hours of 110 ℃ of thermostatic drying chambers, 350 ℃ of roastings 2 hours in Muffle furnace again, finally 350 ℃ of reductase 12s hour in hydrogen, are cooled to room temperature, obtain Pt/TiO
2/ ZSM-5 molecular sieve (catalyst D), wherein, detects auxiliary agent Fe by X-ray photoelectron spectroscopic analysis method: auxiliary agent Pt: host TiO
2: carrier ZSM-5=0.5: 0.005: 4: 100 (weight ratio).
Pressing shown in Fig. 1, is 20m by volume
3(bulk density is 0.66g/ml) catalyst B is arranged in fluid bed, atomize urea solution concentration 50%, and flow is 5m
3/ h, heating carrier gas air air quantity is 100000Nm
3/ h, reaction temperature is at 250 ℃, GHSV (gas space velocity per hour)=5000h
-1, producing ammonia rate is 92.6%.
Comparative example 1: do not add catalyst
Press shown in Fig. 1, spray into pyrolysis tower atomize urea solution concentration 40%, flow is 5m
3/ h, heating carrier gas air air quantity is 100000Nm
3/ h, reaction temperature is at 300 ℃, GHSV (gas space velocity per hour)=5000h
-1, producing ammonia rate is 50.1%.
Comparative example 2: do not add catalyst
Press shown in Fig. 1, spray into pyrolysis tower atomize urea solution concentration 40%, flow is 5m
3/ h, heating carrier gas air air quantity is 100000Nm
3/ h, reaction temperature is at 320 ℃, GHSV (gas space velocity per hour)=5000h
-1, producing ammonia rate is 51.5%.
Claims (5)
1. the catalyst of the isocyanic acid hydrolysis ammonia processed producing in a catalyzing urea pyrolytic process, it is characterized in that, by carrier and the active component host and the doping component auxiliary agent that load on carrier, formed, described carrier is ZSM-5 molecular sieve, described active component host is titanium dioxide, and described doping component auxiliary agent is the mixture of iron, platinum or iron and platinum;
Described catalyst is prepared by the following method:
(1) after ZSM-5 molecular sieve is dry, be dispersed in deionized water to obtain dispersion liquid, by TiO
2precursor liquid A is added drop-wise in described dispersion liquid, after hydrolysis, filters, and washing and precipitating is neutral to pH value, described precipitation roasting is obtained to the molecular sieve of load host; Described TiO
2precursor liquid A is TiCl
4solution or Ti (SO
4)
2solution;
Or by TiO
2precursor liquid B adjust pH to 4～5, add dried ZSM-5 molecular sieve, after dipping 30～45min, lift, and roasting obtains the molecular sieve of load host; Described TiO
2precursor liquid B is Ti (OC
4h
9)
4solution or Ti (OC
3h
7)
4solution;
(2) molecular sieve of described load host is impregnated in the mixing precursor liquid of Fe precursor liquid, Pt precursor liquid or Fe and Pt, floods 12～16 hours, dry roasting, reduces in oxygen-free environment, cooling described catalyst.
2. catalyst according to claim 1, is characterized in that, Fe:Pt:TiO in described catalyst
2: the weight ratio of ZSM-5 molecular sieve is 0～1:0～0.01:2～5:100, and Fe, Pt the two be zero when different.
3. catalyst according to claim 1, is characterized in that, the pH value while being hydrolyzed described in step (1) is 1～3.
4. catalyst according to claim 1, is characterized in that, described in step (1), the time of hydrolysis is 45～60min.
5. catalyst according to claim 1, is characterized in that, the temperature while being hydrolyzed described in step (1) is 70～80 ℃.
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| CN101612575A (en) * | 2009-07-10 | 2009-12-30 | 天津大学 | Fe 2O 3And V 2O 5The use for diesel engine Catalysts and its preparation method of double activity component |
| CN101773837A (en) * | 2010-02-04 | 2010-07-14 | 环境保护部华南环境科学研究所 | Supported SCR denitration catalyst of medium and low temperature flue gas and preparation method and application thereof |
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| CN101773837A (en) * | 2010-02-04 | 2010-07-14 | 环境保护部华南环境科学研究所 | Supported SCR denitration catalyst of medium and low temperature flue gas and preparation method and application thereof |
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