CN1248493A - Methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition - Google Patents

Methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition Download PDF

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Publication number
CN1248493A
CN1248493A CN 98114336 CN98114336A CN1248493A CN 1248493 A CN1248493 A CN 1248493A CN 98114336 CN98114336 CN 98114336 CN 98114336 A CN98114336 A CN 98114336A CN 1248493 A CN1248493 A CN 1248493A
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China
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molecular sieve
methane
indium
oxygen
hzsm5
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CN 98114336
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CN1142025C (en
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王晓东
张涛
马磊
关文
梁东白
林励吾
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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 catalyst is formed from active component and support. It is characterized by that its active component is indium and iron, and its support is molecular sieve, the silicon-aluminium ratio of the molecular sieve is less than 50, the weight percentage content of indium supported by molecular sieve is 0.5-20%, and the weight ratio of molecular sieve and ferric oxide is 10 : 0.5-20. Its preparation method includes the following steps: mechanical-mixing ferric oxide and molecular sieve, supporting the indium salt on the molecular sieve by using immersion method, and roasting at 500-900 deg.C for 3-6 hr. Said invention is suitable for selective reduction of nitrogen oxide compound by using methane in the presence of large amount of oxygen.

Description

A kind of methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition
The present invention relates to gas purification, environmental protection, fields such as Industrial Catalysis, employed catalyst, preparation method and catalytic process when particularly using methane to eliminate oxynitrides (NOx) as reducing agent catalysis.
Oxynitrides (NOx, i.e. NO and NO2) has been subjected to the extensive concern of countries in the world as an aspect of environmental pollution.The 55% fuel combustion product from static father (power station, Industrial Boiler, gas fired-boiler, interior alkene machine and nitric plant etc.) is arranged in the NOx of all dischargings approximately.NH under the oxidizing atmosphere 3Select catalytic reduction of NOx (SCR) to be acknowledged as now from industrial waste gas, to eliminate the effective method of NOx, in Japan and the industrialization of some industrially developed country.But this process NH 3Need the measure control addition, leakage or reaction not exclusively cause secondary pollution easily; The oxidized final generation NH of sulphur-containing substance in the course of reaction 4HSO 4, (NH 4) 2S 2O 7, obstruction, corrosion reaction pipeline, and make catalysqt deactivation.At the problems referred to above and NH 3Storage, equipment and expense that transportation and use etc. are expensive are necessary to explore a kind of without NH 3Make the removing method of reducing agent.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.The patent of USP5149112 points out that under the oxygen-containing atmosphere, an amount of methane is reducing agent, and the Co-ZSM-5 activity of ion-exchange preparation is best.JP06,262,039 proposes under the indium catalyst action that ZSM5 molecular sieve or ferrierite support, and when aerobic existed, reducing agent methane and carbon monoxide acted on simultaneously, can effectively remove oxynitrides, JP06, what 132,139 proposition ZSM5 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 Patent No. points out that for the NO.951120271 patent under the oxidizing atmosphere, methane is made reducing agent, and loaded In/HZSM5 has higher conversion ratio to oxynitrides.
The object of the present invention is to provide a kind ofly under a large amount of oxygen existence conditions, only come the catalyst of selective reduction oxynitrides with methane.
The invention provides a kind of methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition, it is characterized in that: this activity of such catalysts component is indium, iron, indium is supported on the natural or artificial synthetic molecular sieve, the Tie Tong peroxide of iron and molecular sieve mechanical mixture obtain, the silica alumina ratio of molecular sieve is less than 50, the weight percentage of molecular sieve supported indium is 0.5～20%, and the weight ratio of molecular sieve and iron oxide is 10: 0.5～10: 20.
Catalyst provided by the invention can be by the indium salt (In (NO with solubility 3) 3Or InCl 3) adopt immersion process for preparing, 550～900 ℃ of sintering temperatures, 3～6 hours time with the mixture of molecular sieve and iron oxide.Catalyst provided by the invention is eliminated in the reaction at oxynitrides and is used, and is reducing agent with methane only, and [CH4]/[NO] concentration ratio is 0.2～8.0 in the unstripped gas, and reaction temperature is between 350～650 ℃, and the unstripped gas air speed is 1000～100000h -1, reaction pressure is a normal pressure.Reaction temperature the best is between 400～650 ℃, and oxygen concentration the best is between 2.0～10.0%.The present invention is a reducing agent with methane only, is the activity of such catalysts component with indium, iron only, and in very wide temperature range internal reaction function admirable, the oxynitrides conversion ratio can reach more than 90%.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.Below by embodiment in detail the present invention is described in detail.
Embodiment 1 Preparation of catalysts
Here only to contain indium 5% (weight percentage), the weight ratio of molecular sieve and iron oxide is 10: 2 In/HZSM5+Fe 2O 3(silica alumina ratio is 25) describes Preparation of catalysts used among the present invention prevailingly for example.The HZSM5 molecular sieve is provided by Catalyst Factory, Nankai Univ, Fe 2O 3Provide by Nan Shangle chemical plant, Beijing, with 0.4989 gram indium nitrate crystal (In (NO 3) 34.5H 2O) be dissolved in the 5ml deionized water, add 3.0 gram HZSM5 and 0.6 gram Fe again 2O 3Mixture, after fully stirring, left standstill 24 hours, 120 ℃ of bakings 3 hours place 700 ℃ of roastings of muffle furnace 4 hours, before the reaction, with the catalyst compressing tablet, break that to sieve out 40～60 purpose particles standby into pieces.
Methane selective reduction carbon monoxide under embodiment 2 excess oxygens
Here only to contain indium 5% (weight percentage), the weight ratio of molecular sieve and iron oxide is 10: 2 In/HZSM5+Fe 2O 3(silica alumina ratio is 25) describes activity of such catalysts test among the present invention prevailingly for example.Active testing carries out in fixed bed reactors.Before advancing reactor, nitric oxide, methane, oxygen and nitrogen fully mix in blender, catalyst amount 0.5 gram in the active testing, and unstripped gas air speed (GHSV) is 3600h -1, reaction pressure is a normal pressure, reactor places in the temperature control electric furnace, 350～650 ℃ of reaction temperatures.With online chromatography analysis product, catalyst activity is a standard with the conversion ratio (%) that nitric oxide is converted into nitrogen.
The reactivity of embodiment 3 different catalysts
Catalyst Reaction temperature (℃)
??350???400???450???500???550???600????650
?In/HZSM5 In/HZSM5+CuO ??25.1??70.2??95.8??100???99.6??93.4???76.4 ??1.2???3.3???6.8???9.4???15.0??11.2???12.3
?In/HZSM5+Ni 2O 3?In/HZSM5+Co 3O 4?In/HZSM5+Fe 2O 3?Ga/HZSM5+Fe 2O 3?Ga/HZSM5 ??3.0???20.0??36.8??47.7??49.2??44.0??33.4 ??23.2??56.1??86.3??95.6??87.1??72.8??65.7 ??32.3??82.1??99.8??100???100???100???87.4 ??1.2???3.9???8.9???13.6??22.4??25.5??26.4 ??2.0???8.0???24.6??36.5??46.6??50.5??47.3
In(Ga)％＝5％，[HZSM5]∶[MxOy]＝10∶2，GHSV＝3600h -1，
NO=2500ppm, CH 4=2000ppm, O 2=4.0%, He is a balance gas,
Catalyst loading amount 1.0ml, reaction pressure is a normal pressure.The content of embodiment 4 iron oxide is to In/HZSM5+Fe 2O 3The influence of the reactivity of catalyst
Catalyst Reaction temperature (℃)
??350???400???450?????500????550???600???650
In/HZSM5 In/HZSM5+Fe 2O 3(10∶0.5) *In/HZSM5+Fe 2O 3(10∶2) In/HZSM5+Fe 2O 3(10∶4) In/HZSM5+Fe 2O 3(10∶6) In/HZSM5+Fe 2O 3(10∶8) In/HZSM5+Fe 2O 3(10∶10) ??25.1???70.2???95.8????100????99.6??93.4??76.4 ??24.4???78.2???100?????100????100???97.4??84.9 ??32.3???82.1???99.8????100????100???100???87.4 ??29.3???74.2???95.0????100????100???94.0??76.4 ??18.9???59.6???90.1????100????100???94.0??76.4 ??16.5???63.0???94.0????100????100???92.6??72.8 ??17.6???57.6???89.0????100????100???83.3??64.3
*Expression formula in the bracket is represented HZSM5 and Fe 2O 3Weight ratio.
In％＝5％，GHSV＝3600h -1，
NO=2500ppm, CH 4=2000ppm, O 2=4.0%, He is a balance gas,
Catalyst loading amount 1.0ml, reaction pressure is a normal pressure.The content of embodiment 5 indium metal is to In/HZSM5+Fe 2O 3The influence of the reactivity of (10: 2) catalyst
Catalyst Reaction temperature (℃)
??350????400????450????500????550????600????650
HZSM5+Fe 2O 35％In/HZSM5+Fe 2O 310％In/HZSM5+Fe 2O 320％In/HZSM5+Fe 2O 3 ??2.4????12.5????16.4????17.3????15.2????14.3????9.0 ??32.3???82.1????99.8????100?????100?????100?????87.4 ??4.4????19.5????42.7????61.4????70.5????65.4????56.7 ??4.3????18.9????41.2????61.1????70.3????65.4????57.3
NO=2500ppm, CH 4=2000ppm, O 2=4.0%, He is a balance gas,
Catalyst loading amount 1.0ml, reaction pressure is a normal pressure, GHSV=3600h -1Embodiment 6 reaction temperatures are to 5%In/HZSM5+Fe 2O 3The influence of the reactivity of (10: 2) catalyst
Reaction temperature (℃) 400 450 500 550 600 650 NO conversion ratios (%) 82.1 99.8 100 100 100 87.4
NO=2500ppm, CH 4=2000ppm, O 2=4.0%, He is a balance gas, catalyst loading amount 1.0ml, and reaction pressure is a normal pressure, GHSV=3600h -1Embodiment 7 oxygen concentrations are to 5%In/HZSM5+Fe 2O 3The influence of the reactivity of (10: 2) catalyst
Oxygen concentration Reaction temperature (℃)
????350????400????450????500????550?????600????650
??1.0％ ??3.0％ ??5.0％ ????30.8??69.0????86.4???89.8???88.9????85.2???72.5 ????30.0??71.9????89.6???94.2???95.1????94.2????81.8 ????27.1??77.6????92.1???96.1???97.8????94.3????82.8
NO=2500ppm, CH 4=2000ppm, He are balance gas,
Catalyst loading amount 1.0ml, reaction pressure is a normal pressure, GHSV=3600h -1Embodiment 8 air speeds are to 5%In/HZSM5+Fe 2O 3The influence of the reactivity of (10: 4) catalyst
Reaction gas Reaction temperature (℃)
The body air speed ??350?????400?????450?????500????550????600?????650
??3600h -1??7200h -1??10800h -1 ??29.3????74.2????95.0????100????100????94.0????76.4 ??25.2????65.8????95.6????100????100????96.9????79.4 ??21.5????61.7????88.7????100????100????96.1????78.3
NO=2500ppm, CH 4=2000ppm, O 2=4.0%, He is a balance gas,
Catalyst loading amount 1.0ml, reaction pressure is a normal pressure.

Claims (3)

1. methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition, constitute by active component and carrier, it is characterized in that: active component is indium, iron, carrier is a molecular sieve, the silica alumina ratio of molecular sieve is less than 50, the weight percentage of molecular sieve supported indium is 0.5～20%, and the weight ratio of molecular sieve and iron oxide is 10: 0.5～20.
2. described methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition preparation method of claim 1, it is characterized in that: at first with iron oxide and molecular sieve mechanical mixture, again indium salt is supported on the molecular sieve 500～900 ℃ of sintering temperatures, 3～6 hours time with the method for flooding.
3. the described catalyst of claim 1 is used for the excess oxygen methane selective reducing nitrogen-oxygen compound under oxidation, is reducing agent with methane, [CH in the unstripped gas 4]/[NO] concentration ratio is 0.2～8.0, reaction temperature is between 350～650 ℃, oxygen concentration is between 2.0～10.0%.
CNB981143369A 1998-09-23 1998-09-23 Methane selective reducing nitrogen oxide catalyst under oxygen-enriched condition Expired - Fee Related CN1142025C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104906611A (en) * 2015-06-12 2015-09-16 常州大学 Method and device for disinfecting and sterilizing plastic packaging containers
CN107930675A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 Catalyst for cyclohexyl benzene synthesis and preparation method thereof
CN108187732A (en) * 2017-12-12 2018-06-22 哈尔滨工业大学深圳研究生院 A kind of CH of sulfur resistive water resistant4SCR denitration and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104906611A (en) * 2015-06-12 2015-09-16 常州大学 Method and device for disinfecting and sterilizing plastic packaging containers
CN107930675A (en) * 2016-10-13 2018-04-20 中国石油化工股份有限公司 Catalyst for cyclohexyl benzene synthesis and preparation method thereof
CN107930675B (en) * 2016-10-13 2020-03-31 中国石油化工股份有限公司 Catalyst for synthesis of cyclohexylbenzene and preparation method thereof
CN108187732A (en) * 2017-12-12 2018-06-22 哈尔滨工业大学深圳研究生院 A kind of CH of sulfur resistive water resistant4SCR denitration and preparation method thereof
CN108187732B (en) * 2017-12-12 2021-04-02 哈尔滨工业大学深圳研究生院 Anti-sulfur and water-resistant CH4-SCR denitration catalyst and preparation method thereof

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