CN1422694A - Catalyst for reduction of nitrogen oxide, its preparation method and use - Google Patents

Catalyst for reduction of nitrogen oxide, its preparation method and use Download PDF

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Publication number
CN1422694A
CN1422694A CN 01140435 CN01140435A CN1422694A CN 1422694 A CN1422694 A CN 1422694A CN 01140435 CN01140435 CN 01140435 CN 01140435 A CN01140435 A CN 01140435A CN 1422694 A CN1422694 A CN 1422694A
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catalyst
indium
molecular sieve
hzsm
reaction
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CN1151886C (en
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任丽丽
张涛
徐长海
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a catalyst for selectively reducing nitrogen oxide by using methane as reducing agent under the aerobic condition. It is characterized by that the indium is used as active componnet of said catalyst, and supported on HZSM-5 molecular sieve, then the supported In/HZSM-5 molecular sieve catalyst is modified by indium oxide, the silicon-aluminium ratio of the molecular sieve is 5-50, the weight percentage content os indium supported by molecular sieve is 0.5-20%, and the weight ratio of In/HZSM-5 and indium oxide is 2:01-2:10. Said invention uses methane as reducing agent, and has a certain resistance to water, and the conversion rate of nitrogen oxide can be up to above 90%.

Description

A kind of catalyst and method for making and application that is used for reduction of nitrogen oxide
Technical field
The present invention relates to a kind of indium/molecular sieve catalyst that is used for reduction of nitrogen oxide, specifically, relate to a kind of use methane as reducing agent employed catalyst when catalysis in aerobic condition is eliminated oxynitrides (NOx).
The invention still further relates to a kind of this Preparation of catalysts method.
The invention still further relates to this catalyst is the application of reducing agent reduction of nitrogen oxide with methane under aerobic conditions.
Background technology
Oxynitrides (being main air pollutants with nitric oxide and nitrogen dioxide wherein) has been subjected to the extensive concern of countries in the world as an aspect of environmental pollution.Coal and oil are in combustion process, and airborne nitrogen and oxygen can generate a large amount of nitric oxide and a spot of nitrogen dioxide by chemical combination.Nitric oxide is oxidized to nitrogen dioxide subsequently rapidly, and its toxicity is nitric oxide production 5 times.Automobile and chimney can both discharge nitrogen oxide.Nitrogen oxide can form photochemical fog with airborne hydrocarbon under the effect of sunlight, endanger very big.NH3 selects catalytic reduction of NOx (SCR) to realize industrialization in Japan and some industrially developed country under the oxidizing atmosphere.But, just be necessary to explore a kind of removing method of making reducing agent without NH3 because NH3-SCR exists storage, transportation, pipeline obstruction and corrosion and the expensive operating cost of NH3, and easily causes secondary pollution problems.Because natural gas (mainly being methane) reserves are abundant, be widely used in industrial production, and almost be present in the tail gas of each fuel, so, be a practicality and the approach of cheapness with the NOx that discharges in the methyl hydride catalyzed reduction stationary source fuel combustion process.JP06, what 132,139 proposition ZSM-5 were molecular sieve supported is the indium catalyst of auxiliary agent with alkali metal, when aerobic existed, methane is reduction of nitrogen oxide effectively.China's application number points out that for the NO.951120271 patent under the oxidizing atmosphere, methane is made reducing agent, and loaded In/HZSM-5 has higher conversion ratio to oxynitrides; The NO.981143369 patent is pointed out under aerobic conditions, can effectively eliminate NOx with iron oxide decorating molecule sieve as the indium catalyst of supported carrier.But the above-mentioned catalyst activity that provides is also not high, especially under high-speed.
Summary of the invention
The catalyst that the purpose of this invention is to provide a kind of reduction of nitrogen oxide, this catalyst select the catalytic reduction oxynitrides to have very high catalytic activity to methane under aerobic conditions, can remove the oxynitrides in the vehicle exhaust effectively.
Another purpose of the present invention provides a kind of this Preparation of catalysts method.
A further object of the present invention provides the application of this catalyst in reduction of nitrogen oxide.
To achieve these goals, the catalyst of a kind of reduction of nitrogen oxide provided by the invention, active component is an indium, indium is supported on the molecular sieve, the weight content of indium is the 0.5-20% of molecular sieve, and the silica alumina ratio of molecular sieve is 5-50, it is characterized in that, in catalyst, add indium oxide, and the weight ratio that supports the indium oxide of molecular sieve behind the indium and adding is 2: 0.1-2: 10.
In above-mentioned catalyst, molecular sieve is HZSM-5.
Above-mentioned Preparation of catalysts method provided by the invention is with solubility indium salt solution impregnation molecular sieve, and indium is supported on the molecular sieve, and drying is in 550-900 ℃ of following roasting; The indium oxide pressed powder is evenly mixed with the above-mentioned indium molecular sieve mechanical agitation grinding that makes, can be directly used in reaction or carry out roasting.
It is 100-900 ℃ that indium oxide adds the rear catalyst sintering temperature, and roasting time is 0.5-10 hour.
Catalyst provided by the invention mainly is that reducing agent is eliminated nitrogen oxide with methane.Specifically, this reaction can be undertaken by following condition, and [CH4]/[NO] volumetric concentration is than being 0.2-8.0 in the unstripped gas, and reaction temperature is 350-700 ℃, and the unstripped gas air speed is 1000-100000h-1, and reaction pressure is a normal pressure.Reaction temperature the best is 400-650 ℃, and oxygen concentration the best is 2.0-10.0%.
The present invention has following advantage:
1, be reducing agent with methane only, improve the In/HZSM-5 activity of such catalysts with indium oxide, in very wide temperature range internal reaction function admirable, the oxynitrides conversion ratio can reach more than 90%.
2, catalyst provided by the invention has water repelling property preferably, and at high temperature after the water long time treatment, catalytic activity is constant substantially.
3, method for preparing catalyst provided by the invention is simple, and reaction has the good high-temperature reactivity to selectively reducing nitrogen oxides by methane, helps technology and amplifies, and the reaction of commercial Application eliminate to(for) oxynitrides has great Practical significance.
The specific embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not subjected to the restriction of following embodiment:
Embodiment 1, In/HZSM-5/In2O3 Preparation of catalysts
This catalyst mainly makes in two steps, at first obtain In/HZSM-5 with infusion process, wherein In:HZSM-5 is between 0.5%-20%, need 550 ℃-900 ℃ roasting 2-12 hour, adopt mechanical mixing to obtain the In/HZSM5/In2O3 catalyst again, molecular sieve after wherein supporting is 2 with the weight ratio of the In2O3 that the back adds: 0.1-2: 10, and this catalyst can be directly used in reaction or be used further to reaction after roasting 0.5-10 between 100-900 ℃ hour.Here only with In: HZSM-5: In2O3 is that the In/HZSM5/In2O3 (silica alumina ratio is 25) of 1: 20: 5 (percentage by weight) is that example is described Preparation of catalysts used among the present invention prevailingly.The HZSM-5 molecular sieve is provided by Catalyst Factory, Nankai Univ, In2O3 is made by the indium nitrate decomposition, 0.6652 gram indium nitrate crystal (In (NO3) 34.5H2O) is dissolved in the 5ml deionized water, after adding 4.0 grams again HZSM-5 fully stirring, left standstill 24 hours, 120 ℃ were dried by the fire 3 hours, place 700 ℃ of roastings of muffle furnace 6 hours, In (the 5%)/HZSM-5 and the abundant mechanical mixture of 1.0 gram In2O3 that make are stirred, again 600 ℃ of following roastings 6 hours, with catalyst compressing tablet grinding and sieving, it is standby to obtain 32～60 purpose particles at last.
Comparative example 1
Make In (5%)/HZSM-5 catalyst by similarly to Example 1 method, and directly with its compressing tablet grinding and sieving, it is standby to obtain 32-60 purpose beaded catalyst.
Comparative example 2
Configuration 20% In3+ solution adopts equi-volume impregnating to prepare In (10%)/HZSM-5 catalyst by the method step identical with embodiment 1;
Comparative example 3
In2O3 is mixed in 1: 3 ratio with HZSM-5, and 600 ℃ of following roastings 6 hours, at last gained catalyst compressing tablet being sieved, it was standby to obtain 32～60 purpose particles after the abundant mechanical agitation.
Embodiment 2, catalyst be the test of methane selective reduction nitric oxide reactive activity under excess oxygen
Active testing carries out in fixed bed reactors.Before advancing reactor, nitric oxide, methane, oxygen and helium fully mix in blender, catalyst amount 0.8ml in the active testing, and unstripped gas air speed (GHSV) is 3600h-1, reaction pressure is a normal pressure, and reactor places in the temperature control electric furnace, reaction temperature 300-700 ℃.With online chromatography analysis product, catalyst activity is a standard with the conversion ratio (%) that nitric oxide is converted into nitrogen.
Table 1, table 2, table 3, table 4, table 5, table 6, table are used in reaction under the different situations respectively
7, table 8 expression.Simultaneously, the actual conditions of test case 1-8 is also all annotated in table down.
Test result analysis example 1
Comparative example 1 listed by table 1 and embodiment 1 prepared catalyst compares by the catalyst activity property testing that embodiment 2 carries out, show that the adding of In2O3 has improved the ability of catalyst elimination NO effectively, widened its active temperature interval, all reached 100% from the conversion ratio of 500-600 ℃ of NO on this catalyst.
Table 1 indium oxide is to the influence of NO conversion ratio on In (5%)/HZSM-5 catalyst
Catalyst Reaction temperature (℃)
????350 ????400 ????450 ????500 ????550 ????600 ??650 ????700
????In/HZSM-5 ????23.0 ????61.5 ????92.9 ????100 ????93.7 ????83.3 ??71.6 ????49.6
?In/HZSM-5/In 2O 3 ????29.1 ????63.0 ????92.4 ????100 ????100 ????100 ??76.2 ????59.7
In: HZSM-5: In 2O 3=1: 20: 5, GHSV=3600h -1, NO=2500ppm, CH 4=2000ppm, O 2=2.0%, He is a balance gas, catalyst loading amount 0.8ml, and reaction pressure is a normal pressure.
Test result analysis example 2
At catalyst I n/HZSM-5/In 2O 3The weight percentage of In in integer catalyzer is 20% in (1: 20: 5), so the In content that we select multi-form preparation method to make is 20% catalyst and they has been carried out active testing, table 2 has been listed catalyst activity property testing that the prepared catalyst of embodiment 1 and comparative example 1,2 undertakies by embodiment 2 relatively, as seen being all 20% In, (is In/HZSM-5/In when In adopts two kinds of forms (physical mixed behind the dipping earlier) to join in the molecular sieve 2O 3) time, the catalytic activity that catalyst shows is the highest, and the active temperature interval also wants wide many than other two kinds.
The different preparation methods of table 2 are to the influence of indium catalyst activity
Catalyst Reaction temperature (℃)
????350 ????400 ????450 ????500 ????550 ????600 ????650
????In(20％)/HZSM-5 ????19.1 ????44.3 ????63.9 ????82.3 ????82.2 ????70.6 ????61.7
????In/HZSM-5/In 2O 3(1∶20∶5) ????29.1 ????63.0 ????92.4 ????100.0 ????100.0 ????100.0 ????76.2
????In 2O 3/HZSM-4(1∶3) ????24.6 ????63.0 ????84.4 ????90.9 ????89.2 ????88.2 ????62.6
NO=2500ppm, CH 4=2000ppm, GHSV=3600h -1, He is a balance gas, reaction temperature is 400 ℃, and catalyst loading amount 0.8ml, reaction pressure is a normal pressure.
Test result analysis example 3
As shown in Table 3, the influence of the NO conversion ratio of oxygen content change is little, and when oxygen content was 6%, NO was converted into N 2Conversion ratio the highest.
Table 3 oxygen content is to In/HZSM5/In 2O 3The influence of catalyst n O conversion ratio
Oxygen concentration 2％ 4％ 6％ 8％ 10％
NO is converted into N 2(％) 63.01 ?70.79 ?74.33 ?70.52 ?69.23
NO=2500ppm, CH 4=2000ppm, GHSV=3600h -1, He is a balance gas, reaction temperature is 400 ℃, and catalyst loading amount 0.8ml, reaction pressure is a normal pressure.
Test result comparative example 4
The water of adding 2% is handled catalyst I n/HZSM-5/In down in 600 ℃ in reaction gas 2O 3(1: 20: 4) 10 hours, again catalyst is carried out active testing after anhydrating then, table 4 has compared catalyst through the catalytic activity before and after the water treatment relatively, as can be seen from the data, less through water treatment rear catalyst activity change, illustrate that catalyst has certain water-resistance.
Table 4 catalyst I n/HZSM-5/In 2O 3The activity change of water treatment after 10 hours of adding 2% under 600 ℃
Reaction temperature (℃) ????350 ????400 ????450 ????500 ????550 ????600 ????650
Before the water treatment ????29.1 ????63.0 ????92.4 ????100 ????100 ????100 ????76.2
After the water treatment ????31.6 ????64.8 ????91.0 ????100 ????100 ????96.1 ????74.4
NO=2500ppm, CH 4=2000ppm, GHSV=3600h -1, He is a balance gas, reaction temperature is 400 ℃, and catalyst loading amount 0.8ml, reaction pressure is a normal pressure.
Test result analysis example 5
Table 5 has been listed the influence of reaction temperature to catalyst activity, and in the whole temperature range of being investigated, catalyst has all demonstrated good active, and particularly when reaction temperature was between 500 ℃-600 ℃, by response data as can be known, NO was transformed fully.
Table 5 reaction temperature is to In/HZSM5/In 2O 3The influence of the reactivity of (1: 20: 5) catalyst
Reaction temperature (℃) ????400 ????450 ????500 ????550 ????600 ????650
NO conversion ratio (%) ????63.0 ????92.4 ????100 ????100 ????100 ????76.2
NO=2500ppm, CH 4=2000ppm, O 2=2.0%, He is a balance gas, catalyst loading amount 0.8ml, and reaction pressure is a normal pressure, GHSV=3600h -1
Test result analysis example 6
Table 6 has been described the variation of NO concentration to the influence that methane conversion produced, along with the increase of NO concentration, and the corresponding increase of methane conversion.When reaction temperature reached more than 550 ℃, methane just began a large amount of conversions to methyl hydride combustion reaction (NO concentration is 0 o'clock), and this shows that methane is easier on this catalyst and at first reacts with NO.
Table 6 NO concentration is to In/HZSM5/In 2O 3CH on (1: 20: 5) catalyst 4The influence that transforms
NO concentration (ppm) Reaction temperature (℃)
????350 ????400 ????450 ????500 ????550 ????600 ????650 ????700
????0 ????0.00 ????2.06 ????5.03 ????5.35 ????23.76 ????65.48 ????92.51 ????100
????1250 ????8.84 ????26.73 ????30.93 ????39.81 ????48.62 ????59.49 ????79.81 ????100
????2500 ????23.64 ????43.67 ????61.78 ????75.07 ????84.70 ????100 ????100 ????100
CH 4=2000ppm, O 2=2.0%, GHSV=3600h -1, He is a balance gas, catalyst loading amount 0.8ml, and reaction pressure is a normal pressure.
Test result analysis example 7
Table 7 has been described the influence of air speed to this catalyst activity, when air speed from 3600h -1Be increased to 14400h -1The time, catalyst has still demonstrated higher activity, and between 500 ℃-550 ℃, NO still can be transformed fully.
Table 7 air speed is to In/HZSM5/In 2O 3The influence of NO conversion ratio on (1: 20: 5) catalyst
??GHSV(h -1) Reaction temperature (℃)
????350 ????400 ????450 ????500 ????550 ????600 ????650 ????700
????3600 ????29.1 ????63.0 ????92.4 ????100 ????100 ????100 ????76.2 ????59.7
????7200 ????37.0 ????77.2 ????96.4 ????100 ????100 ????90.5 ????72.9 ????57.7
????14400 ????26.5 ????57.2 ????91.7 ????100 ????100 ????92.7 ????78.6 ????61.1
NO=2500ppm, CH 4=2000ppm, O 2=2.0%, He is a balance gas, regulates air speed by changing the He throughput, catalyst loading amount 0.8ml, and reaction pressure is a normal pressure.
Test result analysis example 8
As can be seen from Table 8, along with the increase of reaction velocity, methane conversion reduces gradually on the catalyst.
Table 8 air speed is to In/HZSM5/In 2O 3CH on (1: 20: 5) catalyst 4The influence of conversion ratio
GHSV(h -1) Reaction temperature (℃)
????350 ????400 ????450 ????500 ????550 ????600 ????650 ??700
????3600 ????23.6 ????43.7 ????61.8 ????75.1 ????84.7 ????100 ????100 ??100
????7200 ????20.1 ????40.1 ????55.5 ????64.1 ????75.9 ????90.6 ????100 ??100
????14400 ????13.8 ????28.9 ????46.3 ????55.3 ????62.4 ????77.3 ????100 ??100
NO=2500ppm, CH 4=2000ppm, O 2=2.0%, He is a balance gas, changes air speed by changing the He throughput, catalyst loading amount 0.8ml, and reaction pressure is a normal pressure.

Claims (6)

1, a kind of catalyst that is used for reduction of nitrogen oxide, active component is an indium, indium is supported on the molecular sieve, the weight content of indium is the 0.5-20% of molecular sieve, the silica alumina ratio of molecular sieve is 5-50, it is characterized in that, in catalyst, add indium oxide, and the weight ratio that supports the indium oxide of molecular sieve behind the indium and adding is 2: 0.1-2: 10.
2, catalyst as claimed in claim 1 is characterized in that, described molecular sieve is HZSM-5.
3, a kind of method for preparing the described catalyst of claim 1 is characterized in that, with solubility indium salt solution impregnation molecular sieve, indium is supported on the molecular sieve, and drying is in 550-900 ℃ of following roasting; The indium oxide pressed powder is evenly mixed with the above-mentioned I indium molecular sieve mechanical agitation grinding that makes, can be directly used in reaction or carry out roasting.
4, preparation method as claimed in claim 3 is characterized in that, it is 100-900 ℃ that described indium oxide adds the rear catalyst sintering temperature, and roasting time is 0.5-10 hour.
5, a kind of claim 1 or 3 described Application of Catalyst is characterized in that, [CH4]/[NO] volumetric concentration is than being 0.2-8.0 in the unstripped gas, reaction temperature is 350-700 ℃, the unstripped gas air speed is 1000-100000h-1, and reaction pressure is a normal pressure, and oxygen concentration the best is 2.0-10.0%.
6, Application of Catalyst as claimed in claim 5 is characterized in that, reaction temperature the best is 400-650 ℃.
CNB011404353A 2001-12-06 2001-12-06 Catalyst for reduction of nitrogen oxide, its preparation method and use Expired - Fee Related CN1151886C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321742C (en) * 2003-11-13 2007-06-20 南京大学 Visible light response photocatalyst and application thereof
CN104492478A (en) * 2014-11-21 2015-04-08 常州大学 Preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst
CN104707590A (en) * 2013-12-13 2015-06-17 中国科学院大连化学物理研究所 Preparation method and application of morphology-controllable indium nanocatalyst

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321742C (en) * 2003-11-13 2007-06-20 南京大学 Visible light response photocatalyst and application thereof
CN104707590A (en) * 2013-12-13 2015-06-17 中国科学院大连化学物理研究所 Preparation method and application of morphology-controllable indium nanocatalyst
CN104492478A (en) * 2014-11-21 2015-04-08 常州大学 Preparation method of a phosphoric acid modified microporous molecular sieve shape-selective catalyst

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