CN1340372A - Low-temp catalytic process for removing nitroxide, ammonia, CO and hydrogen from industrial gas or waste gas - Google Patents

Low-temp catalytic process for removing nitroxide, ammonia, CO and hydrogen from industrial gas or waste gas Download PDF

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Publication number
CN1340372A
CN1340372A CN 00122945 CN00122945A CN1340372A CN 1340372 A CN1340372 A CN 1340372A CN 00122945 CN00122945 CN 00122945 CN 00122945 A CN00122945 A CN 00122945A CN 1340372 A CN1340372 A CN 1340372A
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ammonia
catalyst
low
gas
ppm
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CN1190255C (en
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吴迪镛
秦永生
王树东
付桂芝
袁权
张金昌
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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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Abstract

A low-temp. catalytic process for removing Nox, NH3, CO and H2 from the industrial gas or waste gas containing O2 (3-20%), No (5-1000 ppm), CO2 (0.05-25%), Co (0.01-0.6%), H2 (0.01-0.5%), H2O (0.1-30% and SO2 (0-50 ppm) features that a non-uniformly distributed egg shell type catalyst with low content of noble metal is used, which is composed of carrier (alpha-Al2O3) and active component Pd and/or Pt). After the NH3 (with NH3/NO=1-3 is proportionally added to the industrial or waste gas, the NOx, NH3, Co and H2 can be removed at 160-280 deg.C down to below 10 ppm. Its advantages include high removal rate, low consumption of NH3 and nobble metal, and no secondary ammonia pollution.

Description

Method for low-temperature catalytic removal of nitrogen oxides, ammonia, carbon monoxide and hydrogen from industrial gas or waste gas
The invention relates to the fields of environmental protection, industrial catalysis, gas purification and the like. For the first timeProvides a strip of active non-uniform Pd and/or Pt (-M)/Al2O3On the catalyst, under the condition of oxygen enrichment and carbon dioxide, ammonia is partially selectively catalyzed and reduced to remove NO and catalyzed and oxidized to remove reducing agent (NH)3、CO、H2) The new approach of (1).
In the chemical, electrical and other industries, a large amount of NO-containing exhaust gas is emitted to the atmosphere. NO can form environmental problems such as acid rain, photochemical smog, photochemical pollution and the like through a series of changes, and great damage is caused to human and ecological environment. The treatment of NO in exhaust gases is becoming increasingly important. The method for partial selective catalytic reduction of NO by ammonia is one of the methods for removing NO, and generally, ammonia with the stoichiometric ratio equal to or more than that of the ammonia which is subjected to chemical reaction with NO is added into exhaust gas on a noble metal or non-noble metal catalyst (Pd, Pt, Rh, V, Cu and Cr) so that the NO is basically and completely reacted to achieve the purpose of removing NO. This process has significant disadvantages:
(1) the ammonia addition amount is difficult to control, and secondary pollution of ammonia or a device for purifying ammonia is easy to cause;
(2) the reaction temperature is higher, and the energy is difficult to recover;
(3) the catalyst is not resistant to sulfur dioxide and is easy to be poisoned;
(4) not applicable to NO and reducing agent (NH)3、CO、H2) The deep purification process of (1).
The invention aims to provide a method for low-temperature catalytic removal of NO from industrial gas or waste gasx、NH3、CO、H2The method has high NO removal rate, wide operation temperature range and can simultaneously remove the reducing agent (NH)3、CO、H2) The method has the advantages of less consumption of noble metal catalyst, simple flow and convenient operation.
The invention provides a method for removing NO from industrial gas or waste gas by low-temperature catalysisx、NH3、CO、H2The method of (2), characterized by:
takes a non-uniform eggshell type catalyst with low noble metal content as a catalyst, and the catalyst takes α -Al2O3SheetTaking the single crystal as a carrier, and taking 0.05-0.5 wt% of Pd and/or Pt as an active component;
at O2＝3-20％、NO＝5-1000ppm、CO2＝0.05-25％、CO＝0.01-0.6％、H2＝0.01-0.5％、H2O＝0.1-30％，SO2NH is added to exhaust gas of 0-50ppm3Gas with a mixing amount of H3Under the condition of 160-280 ℃, NO and NH are removed simultaneously3、CO、H2To below 10 ppm.
0.01-10 wt% of auxiliary agent can be added into the catalyst, the auxiliary agent is selected from one of Sr, Mg, Ca, Mn, Cr, V and Zn, and the active component and the auxiliary agent are non-uniformlydistributed on the carrier in an eggshell shape.
The principle of the invention is to utilize active non-uniform distribution of Pd and/or Pt (-M)/Al2O3On the catalyst, the NO reduction reaction of ammonia is dominant in the parallel competition process of the reaction with ammonia oxygen, thereby realizing the process of selectively reducing and removing NO from the ammonia part under the oxygen-enriched condition and simultaneously removing the reducing agent (NH) by catalytic oxidation under the oxygen-enriched condition3、CO、H2). The selectivity of reducing NO by ammonia is high at normal pressure and low temperature (160-280 ℃), and the NO removal rate is up to more than 99%; NH (NH)3、CO、H2The conversion rate of oxidation is higher than 99%; the main reaction is as follows:
I
II
III
IV reaction I is NO reduction reaction, and reactions II, III and IV are reducing agents (NH)3、CO、H2And) oxidation reaction. After the reaction is initiated, ammonia is simultaneously distributed to NO and O2To carry outReduction and aminooxy reactions. The key to this process is to control the temperature to ensure that there is sufficient ammonia and NO to undergo the reduction reaction I and that there is sufficient oxygen and reductant (NH)3、CO、H2) Carrying out oxidation reactions II, III and IV.
The invention adopts the same preparation method of catalyst with patent application number 98114397.0 to prepare low-platinum-palladium-content active non-uniform Pd and/or Pt (-M)/Al with Pd and/or Pt as main active components2O3A catalyst. Taking phi 2-3 mm and the strength not less than 5kgf/cm2The spherical alumina is used as carrier, the carrier is presaturated and adsorbed by oxygen-containing organic compound, the pretreated carrier is soaked in noble metal solution, and then high-temp. roasting is carried outAfter burning and cooling, the mixture is reduced by hydrazine solution, washed and dried. The catalyst has the advantages of high activity, low-temperature stability, good multiple startability and small consumption of noble metal. The dosage of the noble metal is only 0.05-0.5%, which is 5-10 times lower than that of the noble metal of the common catalyst, thereby greatly reducing the price of the catalyst.
The invention adopts ammonia as part of selective reducing agent, and the amount of ammonia added is adjusted according to the highest content of nitrogen oxide in the waste gas. NOxThe amount is high, and the amount of the added ammonia is high; on the contrary, the ammonia amount can be low or constant. Wide range of ammonia amount to be added NH31-3 of/NO. The dosage of the reducing agent is easy to control, and the control cost and the secondary pollution of the reducing agent are effectively reduced. The ammonia can be liquid ammonia, crude ammonia or waste ammonia, so that the cost of the reducing agent can be reduced.
The invention is described in detail below by way of examples:
example 1:
taking phi 2-3 mm and the strength is more than or equal to 5kgf/cm220g of the spherical alumina used as a carrier, and the carrier was subjected to presaturation adsorption treatment with40% of acetaldehyde, an oxygen-containing organic compound, for 12 hours. Weighing 100mg platinum and palladium, dissolving in 1ml aqua regia, controlling the volume at 20ml, soaking 20g pretreated carrier in the solution for 5 min, heat treating at 500 deg.C for 20 min, calcining at 500 deg.C for 4 hr, cooling, and reducing the catalyst with 1% hydrazine solutionAnd (4) after the agent is completely reduced, cleaning and drying. The catalyst is used in the reaction of example 6, and has high NO eliminating rate at normal pressure and low temperature, NO converting rate at 200 deg.c higher than 99%, and outlet of NO and NH3Are all less than 10 ppm.
Example 2:
50 g of the same carrier as in example 1 was taken, and the carrier was presaturated with 35% ethanol solution for adsorption treatment for 12 hours, and 50mg of Pd and/or PtCl was added2，0.03gSrCO3Dissolving with 3ml, controlling volume to 50ml, soaking the treated carrier in the solution for 2 min, heat treating at 1200 deg.C for 10 min, calcining at 800 deg.C for 2 hr, cooling, reducing the catalyst with 1% hydrazine solution for 12 hr, washing with chlorine radical, alkalinity and impurity, and drying. The catalyst is filled in the same reaction equipment as example 3, under the same experimental conditions as example 3, at 200 ℃, the NO conversion rate is higher than 99 percent, and the NO and NH are discharged3Are all smallAt 10 ppm.
Example 3:
taking phi 2-3 mm and the strength is more than or equal to 5kgf/cm211000 g of the spherical alumina carrier, and carrying out presaturation adsorption treatment on the carrier by using 40 percent of oxygen-containing organic compound acetaldehyde for 12 hours. Weighing 10 mg of platinum and palladium, completely dissolving the platinum and palladium by aqua regia, wherein the volume of the platinum and palladium is 50ml, soaking the pretreated carrier into the solution for 1 minute, carrying out high-temperature heat treatment at 1200 ℃ for 10 minutes, roasting at 800 ℃ for 4 hours, cooling, reducing the catalyst by using a 1% hydrazine solution, and cleaning and drying after complete reduction. Obtaining the active non-uniform catalyst with the Pd and/or Pt content of 0.05 percent; an active non-uniform catalyst with a Pd and/or Pt content of 0.05% was also obtained in the same way. The two catalysts are filled in the same reaction equipment as example 5, and under the same experimental conditions as example 5, the NO conversion rate at 200 ℃ is higher than 99%, and the output NO and NH are obtained3Are all less than 10 ppm.
Example 4:
the same carrier 50 g as in example 3 was used to prepare Mg/Al with a Mg content of 0.405% in the same manner as in example 32O3A catalyst. The catalyst was loaded in the same reaction apparatus as in example 5In preparation, under the same experimental conditions as in example 5, the NO conversion rate at 200 ℃ is higher than 99%, and the output NO and NH are obtained3Are all less than 10 ppm.
Example 5:
a normal pressure, fixed bed reactor was charged with 1 gram of 0.2% active non-uniformly distributed Pd and/or Pt/Al as prepared in example 32O3Catalyst, experimental conditions: NO 1000 ± 20ppm, NH3＝1000-2000ppm，O2＝3-10％，CO20.05-15% of N2S.v. 2500ml/g hr, the results of NO conversion and ammonia and nitrogen oxide content in the tail gas as a function of temperature are obtained as in table 1.
TABLE 1 NO removal Rate, Outlet NO and NH under different temperature conditions3
Temperature (. degree.C.) 150 160 200 220 250
RNO(％) 95.6 99.2 99.6 99.6 99
NO(ppm) 44 8 4 4 10
NH3(ppm) Can not be detected Can not be detected Can not be detected Can not be detected Can not be detected
As can be seen from this table, NH was added at 160 to 250 ℃3After complete reaction, the residual NO in the waste gas is less than 10ppm, ammonia can not be detected (the lowest detected amount of ammonia is 10ppm), and the NO removal rate is higher than 99%.
Example 6:
1 g of 0.5% active non-homogeneously distributed Pd and/or Pt catalyst prepared in example 1 was charged in a normal pressure, fixed bed reactor under experimental conditions: NO 1000 ± 20ppm, NH3＝1000-1700ppm，O2＝10％，CO2＝15％，H2O is 0.1-17%, and the rest is N2And S.V. 2000 ml/g.hr, the temperature is 220-250 ℃, the NO removal rate is higher than 99%, and ammonia cannot be detected (the lowest detection amount of ammonia is 10 ppm).
Example 7:
a constant pressure, fixed bed reactor was charged with 20 grams of 0.1% active, non-uniformly distributed Pd and/or Pt/Al as prepared in example 42O3Catalyst, experimental conditions: NO 5-600ppm, NH3＝1000-1700ppm，O2＝10％，CO2＝15％，H2O is 0.1-30% and the rest is N2S.V. ═ 2000ml/g hr, NO and NH were obtained at a temperature ranging from 220 to 250 ℃3The removal rate is higher than 99%, and ammonia can not be detected (the lowest detected amount of ammonia is 10 ppm).
Example 8:
a constant pressure, fixed bed reactor was charged with 20 grams of 0.2% active, non-uniformly distributed Pd and/or Pt/Al as prepared in example 22O3Catalyst, experimental conditions: 5-600ppm of NO, 0.1-0.6% of CO and NH3/NO＝1-3，O2＝10％，CO215% of the rest is N2S.V. ═ 2000ml/g hr, at 200 ℃ NO, CO, NH3The conversion rate is higher than 99 percent, and NO, CO and NH are discharged3Are all less than 10 ppm.
Example 9:
under the same conditions of reaction equipment, catalyst, gas composition and reaction space velocity as those of the embodiment 8, 0.1-0.6% of H is added2Gas, 200 ℃ and 250 ℃, NO and H2、CO、NH3The conversion rate is higher than 99 percent, and NO and H are discharged2、CO、NH3Are all less than 10 ppm.
Example 10:
a constant pressure, fixed bed reactor was charged with 20 grams of 0.1% active, non-uniformly distributed Pd and/or Pt/Al as prepared in example 42O3Catalyst, experimental conditions: NO 600. + -. 20ppm, NH3＝1000-1800ppm，O2＝10％，CO215% of the active non-uniform Pd and/or Pt/Al, 20g of 0.1% prepared in example 4, were charged in a fixed bedreactor at atmospheric pressure2O3Catalyst, experimental conditions: NO 600. + -. 20ppm, NH3＝1000-1800ppm，O2＝10％，CO2＝15％，20～60ppmSO2，0.6％CO，0.3％H2The remainder being N2S.V. ═ 2000ml/g hr, at 230 ℃ and 280 ℃, the NO conversion rate is higher than 99 percent, and NO and NH are discharged3、CO、H2Are all less than 10 ppm.
Example 11:
a constant pressure, fixed bed reactor was charged with 20 grams of 0.1% active, non-uniformly distributed Pd and/or Pt/Al as prepared in example 32O3Catalyst, experimental conditions: NC 600-700 ppm, NH3＝1000～2000ppm，O2＝10％，CO2＝15％，CO＝0.1-0.6％，H2＝0.1-0.3％，H2O＝0.1-0.2％，SO220 to 50ppm, and the balance of N2S.V. -. 2000 ml/g.hr, stable operation over 500 hours, catalyst stability results at 200 ℃ and 280 ℃, NO, NH3，CO，H2The conversion rate is higher than 99 percent, and NO and NH are discharged3、CO、H2Are all less than 10 ppm.
Example 12:
10000 g of 0.1% active non-uniform Pd and/or Pt/Al prepared in example 3 are filled in a normal pressure fixed bed reactor2O3Catalyst, experimental conditions are Shanghai Bao steel lime kiln tail gas: NO 7-800 ppm, NH3＝247～856ppm，O2＝11-13％，CO2＝12-18％，CO＝0.1-0.6％，H21-5% of O and the balance of N2S.v. ═ 2450ml/g · hr, stable operation over 200 hours, 200 hStability results of catalyst at-250 ℃, NO, NH3CO, conversion rate higher than 99%, and NO and NH at the outlet3And CO is less than 10 ppm.

Claims (3)

1. Low-temperature catalytic removal of NO from industrial gas or waste gasx、NH3、CO、H2The method of (2), characterized by:
takes a non-uniform eggshell type catalyst with low noble metal content as a catalyst, and the catalyst takes α -Al2O3Independently used as a carrier, and 0.05-0.5 wt% of Pd and/or Pt is used as an active component;
at O2＝3-20％、NO＝5-1000ppm、CO2＝0.05-25％、CO＝0.01-0.6％、H2＝0.01-0.5％、H2O＝0.1-30％，SO2NH is added to exhaust gas of 0-50ppm3Gas with a feed rate of NH31-3, and simultaneously removing NO and NH at the temperature of 160-280 DEG C3、CO、H2To below 10 ppm.
2. Low-temperature catalytic removal of NO from industrial gases or exhaust gases according to claim 1x、NH3、CO、H2The method of (2), characterized by: 0.01-10 wt% of auxiliary agent is added into the catalyst, the auxiliary agent is selected from one of Sr, Mg, Ca, Mn, Cr, V and Zn, and the active component and the auxiliary agent are non-uniformly distributed on the carrier in an eggshell shape.
3. Low-temperature catalytic removal of NO from industrial gases or exhaust gases according to claim 1x、NH3、CO、H2The method of (2), characterized by: the ammonia is liquid ammonia, crude ammonia or waste ammonia.
CNB001229451A 2000-08-30 2000-08-30 Low-temp catalytic process for removing nitroxide, ammonia, CO and hydrogen from industrial gas or waste gas Expired - Fee Related CN1190255C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101081303B (en) * 2007-06-28 2010-12-01 湖南科技大学 Method for fathering submarine discharge gas through air self-cleaning
CN102423629A (en) * 2010-07-08 2012-04-25 气体产品与化学公司 Treatment of flue gas from an oxyfuel combustion process
CN102698742A (en) * 2012-05-18 2012-10-03 中国科学院宁波材料技术与工程研究所 Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same
CN110327918A (en) * 2019-07-15 2019-10-15 北京工业大学 It is a kind of to remove NH simultaneously3Catalyst and the preparation of escape and CO
CN116422343A (en) * 2023-04-11 2023-07-14 中国科学院山西煤炭化学研究所 Double-atom catalyst for removing smoke pollutants, preparation method thereof, layered combination catalyst combination and application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101081303B (en) * 2007-06-28 2010-12-01 湖南科技大学 Method for fathering submarine discharge gas through air self-cleaning
CN102423629A (en) * 2010-07-08 2012-04-25 气体产品与化学公司 Treatment of flue gas from an oxyfuel combustion process
CN102698742A (en) * 2012-05-18 2012-10-03 中国科学院宁波材料技术与工程研究所 Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same
CN110327918A (en) * 2019-07-15 2019-10-15 北京工业大学 It is a kind of to remove NH simultaneously3Catalyst and the preparation of escape and CO
CN116422343A (en) * 2023-04-11 2023-07-14 中国科学院山西煤炭化学研究所 Double-atom catalyst for removing smoke pollutants, preparation method thereof, layered combination catalyst combination and application
CN116422343B (en) * 2023-04-11 2024-03-05 中国科学院山西煤炭化学研究所 Double-atom catalyst for removing smoke pollutants, preparation method thereof, layered combination catalyst combination and application

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