CN101480615A - Catalyst for decomposing laughing gas and preparation method thereof - Google Patents
Catalyst for decomposing laughing gas and preparation method thereof Download PDFInfo
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- CN101480615A CN101480615A CNA2009100797249A CN200910079724A CN101480615A CN 101480615 A CN101480615 A CN 101480615A CN A2009100797249 A CNA2009100797249 A CN A2009100797249A CN 200910079724 A CN200910079724 A CN 200910079724A CN 101480615 A CN101480615 A CN 101480615A
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Abstract
The invention relates to a catalyst for catalytic decomposition of nitrous oxide in industrial waste gas and the preparation method of the catalyst, belonging to the field of development of industrial catalysts. The prior catalysts have the disadvantages of sensitivity for impurities in waste gas, easy loss of activity caused by poisoning, short service life and expensive price. The catalyst for catalytic decomposition of the nitrous oxide in the industrial waste gas belongs to a carrying type catalyst, wherein Al2O3 or dichroite is used as a carrier, one of or a plurality of metallic oxides of IIA, IIB and VIII are used as active components, Ni and Pt are preferably selected as the main active components of the catalyst, and Co and Mg are preferably selected as the auxiliary active components of the catalyst; the content of the main active components of the catalyst is 0.01 to 15.0 percent (wt) of the total content of the catalyst, and the content of the auxiliary active components of the catalyst is 0.0 to 20.0 percent (wt) of the total content of the catalyst. The method of immersion is used for preparing the catalyst in the following steps: firstly, the carrier is used for immersing the auxiliary active components of the catalyst, and then, the main active components of the catalyst after being dried are immersed; finally, the catalyst is obtained after the processes of drying and roasting. The catalyst for catalytic decomposition of the nitrous oxide in the industrial waste gas has the advantages of highly effective decomposability, high stability, low price and the like.
Description
Technical field
The invention belongs to the industrial catalyst development field, be specifically related to that laughing gas is loaded catalyst of nitrogen and oxygen and preparation method thereof in a kind of catalytic decomposition industrial waste gas.
Background technology
Along with expanding economy; people improve constantly the material life quality; the kind of chemical products is various day by day; the quality of product improves constantly; big industrialization degree improves gradually, and big suitability for industrialized production is serious day by day to the destruction that environment causes, and the environment that the mankind depend on for existence has been subjected to heavy damage; the protection environment, preventing the pollution of the environment is subjected to the great attention of countries in the world, and the human environment of depending on for existence of the protection of actively taking action.Waste gas in the industrial processes usually contains nitrogen oxide, comprising nitric oxide (NO), nitrogen dioxide (NO
2), laughing gas (N
2O).NO, NO in the industrial waste gas
2The method that can adopt water to absorb reclaims, utilize and reach the purified treatment purpose.N
2O is that colourless nothing is smelt, and chemical property is stable, is difficult for being cleaned processing, lacks maturation in the past always, effectively reduces discharging the treatment process technology, causes and contains N
2The industrial waste gas of O is arranged to atmosphere without any processing, and N
2O is to earth atmosphere one of the most serious gas that works the mischief, it under action of ultraviolet radiation with air in the oxygen reaction form photochemistry poisonous substance and N
2What O was serious damages the ozone layer, and has tangible greenhouse effects again simultaneously, studies show that its greenhouse effects are about 300 times of carbon dioxide, therefore the N in control and the elimination industrial production waste gas
2O is to big-and-middle gas discharging the having caused great attention of countries in the world.And actively administer research.At present the laughing gas treatment technology is mainly contained:
1, high-temperature decomposition
With N
2O sends in the high temperature reaction stove together with the fuel gas that contains the low-carbon (LC) hydro carbons, under greater than 1000 ℃ of pyroreaction conditions, and N
2O and low-carbon (LC) hydro carbons carry out chemical reaction, wherein N
2O is converted into nitrogen, hydrocarbon compound and then is converted into carbon dioxide and water (US 6328941; US 4973457; US 5429811; US 6056928), reaction equation is as follows:
N in this technology purified industrial waste gas
2O need carry out being higher than under 1000 ℃ the temperature, consumes a large amount of HC fuel in the processing procedure, causes the new wasting of resources; While reaction temperature height, also very harsh to the requirement of equipment, equipment investment is higher.
2, catalytic reduction method
Under the effect of catalyst, under less than 600 ℃ temperature conditions, be that reducing agent is nitrogen G﹠W (CN1660492 with conversion of nitrogen oxides usually with ammonia; CN1903412; CN101011659; CN101028594; US 5736114), its representative reactions equation is:
This technology needs to add reducing agent such as ammonia etc. in course of reaction, and operating condition strictness in the purification process is easy to generate secondary pollution, and catalyst is strict to impurities in waste gas, and poisoning easily loses activity the poor stability of catalyst.
3, catalytic decomposition method
Usually under reaction temperature is lower than 700 ℃ condition, the direct catalytic decomposition of laughing gas is become nitrogen and oxygen (CN1102435C; CN11088505C; CN120919C; WO9852681), its representative reactions equation is:
This catalyst directly makes N
2O is decomposed into nitrogen and oxygen, and catalyst is strict to impurity content in the flue gas, and catalyst moves easy sintering under hot conditions, and loses activity, and catalyst life is short usually less than 2 years, and the expense of catalyst is very high, and the production run cost is increased substantially.
Summary of the invention
The objective of the invention is to solve the problems of the prior art, a kind of purified industrial waste gas is provided, Catalysts and its preparation method that can the catalytic decomposition laughing gas.
Laughing gas is that nitrogen and oxygen catalyst are loaded catalyst in the catalytic decomposition industrial waste gas provided by the invention, wherein carrier is alundum (Al or cordierite, catalyst activity consists of major catalyst active component and co-catalyst active component, is in IIA, IIB, the VIII family element one or more.The mass content of major catalyst active component in catalyst is that 0.01～15.0% (wt), the mass content of co-catalyst active component content in catalyst are 0.0～20.0% (wt).
The present invention also provides the preparation method of this solid catalyst to adopt step impregnation method to prepare the supported solid catalyst, and concrete preparation process is as follows:
1) at first measures water absorption rate under dry catalyst carrier room temperature, the condition of normal pressure.
2) major catalyst active component, co-catalyst active component soluble-salt are mixed with certain concentration solution.
3) with Al
2O
3During for carrier, carrier generally needs to carry out roast under 600～800 ℃ of conditions and handles; When being carrier with the cordierite, cordierite needs to pulverize earlier, screening obtains 40～60 order particles, and the cordierite particle surface need carry out Al
2O
3After coating preliminary treatment, drying and the roasting as the carrier of catalyst.
4) claim (amount) to get the salting liquid of quantitative carrier, co-catalyst active component, carry out the dipping of co-catalyst active component, flood at ambient temperature after 0.5～12.0 hour and filter, filter residue forced air drying after 3～10 hours in 95～120 ℃ of baking ovens, flood major catalyst active constituent 0.1～1.0 again, forced air drying is after 3～10 hours in 95～120 ℃ of baking ovens, and wearing out in 500～600 ℃ of muffle furnaces promptly got the catalyst for preparing in 2～4 hours.
The specific embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
With cordierite (400 hole/inches
2) grind the back screening and obtain 40～60 order solid particles, washed after the preliminary treatment under 110 ℃ of conditions forced air drying 3 hours, dipping Al
2O
3Colloidal sol is modified carrier, and forced air drying is 10 hours under 105 ℃ of conditions, and roasting 2h obtains catalyst carrier under 650 ℃ of conditions.
Take by weighing cobalt nitrate [Co (NO
3)
26H
2O] 9.2g, be dissolved in the 200mL distilled water, obtain cobalt nitrate solution; Take by weighing the carrier of 100g preparation, place the cobalt nitrate solution dipping to filter after 12.0 hours, filter residue forced air drying in 110 ℃ of baking ovens obtained catalyst precursor I in 3 hours.
Take by weighing nickel nitrate [Ni (NO
3)
26H
2O] 21.5g is dissolved in the 200mL distilled water, obtains nickel nitrate solution; Place nickel nitrate solution to filter after 0.5 hour above-mentioned catalyst precursor I, filter residue forced air drying 5 hours in 110 ℃ of baking ovens, roasting is 4 hours in 550 ℃ of muffle furnaces, obtains catalyst for decomposing laughing gas I.
The catalyst I that takes by weighing 1g preparation places fixed bed reactors, at 450 ℃, gas composition 0.25% (v) N
2Under the experiment condition of O+ nitrogen, gas volume air speed 2000mL/g.hr, N
2The O rates of decomposing and transforming is 94.5%.
Embodiment 2
With cordierite (400 hole/inches
2) grind the back screening and obtain 40～60 order solid particles, washed after the preliminary treatment under 110 ℃ of conditions forced air drying 3 hours, dipping Al
2O
3Colloidal sol is modified carrier, and forced air drying is 4.5 hours under 100 ℃ of conditions, and roasting 2h obtains catalyst carrier under 600 ℃ of conditions.
Take by weighing cobalt nitrate [Co (NO
3)
26H
2O] and [Ca (NO
3)
26H
2O] 10.0g and 3.5g, be dissolved in the 200mL distilled water, obtain cobalt nitrate+calcium nitrate solution; The carrier of the 100g that takes by weighing preparation places the cobalt nitrate solution dipping to filter after 10 hours, filter residue and in 95 ℃ of baking ovens forced air drying obtained catalyst precursor II in 12 hours.
Take by weighing chloroplatinic acid [H respectively
2PtCl
66H
2O] and nickel nitrate [Ni (NO
3)
26H
2O] 2.5g and 20.0g, be dissolved in the 200mL distilled water, obtain containing nickel nitrate and platinum acid chloride solution, place nickel nitrate+platinum acid chloride solution solution dipping to filter after 0.1 hour catalyst precursor II, filter residue forced air drying 8 hours in 100 ℃ of baking ovens, roasting 3 hours in 550 ℃ of muffle furnaces again obtains catalyst for decomposing laughing gas II.
The catalyst I I that takes by weighing 1g preparation is in fixed bed reactors, at 450 ℃, gas composition 0.25% (v) N
2Under the experiment condition of O+ nitrogen, gas volume air speed 3000mL/g.hr, N
2The O rates of decomposing and transforming is 99.8%.
Embodiment 3
Take by weighing cobalt nitrate [Co (NO respectively
3)
26H
2O], magnesium nitrate [Mg (NO
3)
26H
2O] and Xiao Suan ?8.6g, 10.4g and 6.4g, be dissolved in the 200mL distilled water, obtain containing cobalt nitrate and magnesium nitrate solution; Take by weighing the Al that 600 ℃ of roasts are handled
2O
3Carrier 100g places cobalt nitrate+magnesium nitrate solution, floods after 10 hours to filter, and filter residue forced air drying 12 hours in 95 ℃ of baking ovens obtains catalyst precursor III; Take by weighing 12.8g nickel nitrate [Ni (NO
3)
26H
2O], be dissolved in the 200mL distilled water, obtain nickel nitrate solution, with catalyst precursor III place nickel nitrate solution dipping 2.0 hours, filtration, filter residue 100 ℃ of dryings 10 hours, roasting is 3 hours in 550 ℃ of muffle furnaces, obtains catalyst for decomposing laughing gas III.
The catalyst I II that takes by weighing 1g preparation in fixed-bed reactor, (the v) N that forms 1.35% at 300 ℃, gas volume
2O+1.8% (v) O
2+ 1.01% (v) CO+3.5% (v) CO
2+ 0.02% (v) NO+0.01% (v) NO
2+ 2.5% (v) H
2O+0.03% (v) SO
2Under the experiment condition of+nitrogen, gas volume air speed 2000mL/g.hr, N
2The O rates of decomposing and transforming is 69.8%.
Embodiment 4
Take by weighing cobalt nitrate [Co (NO respectively
3)
26H
2O] and magnesium nitrate [Mg (NO
3)
26H
2O] 10.3g and 10.4g, be dissolved in the 200mL distilled water, obtain containing cobalt nitrate and magnesium nitrate solution; Take by weighing 650 ℃ of roasts and handle Al
2O
3Carrier 100g places cobalt nitrate+magnesium nitrate solution, floods after 0.5 hour to filter, and filter residue forced air drying 12 hours in 95 ℃ of baking ovens obtains catalyst precursor IV.
Take by weighing 2.2g chloroplatinic acid [H
2PtCl
66H
2O] be dissolved in the 200mL distilled water, obtain platinum acid chloride solution; VI places platinum acid chloride solution with catalyst precursor, flood after 0.1 hour to filter, and filter residue forced air drying 10 hours in 105 ℃ of baking ovens, roasting 3 hours in 550 ℃ of muffle furnaces again obtains catalyst for decomposing laughing gas IV.
Take by weighing 1g catalyst I V, (the v) N that forms 1.35% at 300 ℃, gas volume
2O+1.8% (v) O
2+ 1.01% (v) CO+3.5% (v) CO
2+ 0.02% (v) NO+0.01% (v) NO
2+ 2.5% (v) H
2O+0.03% (v) SO
2Under the experiment condition of+nitrogen, gas volume air speed 2000mL/g.hr, N
2The O rates of decomposing and transforming is 73.7%.
Embodiment 5
Take by weighing cobalt nitrate [Co (NO respectively
3)
26H
2O] and magnesium nitrate [Mg (NO
3)
26H
2O] 7.1g and 5.7g, be dissolved in the 200mL distilled water, obtain containing cobalt nitrate and magnesium nitrate solution; Take by weighing the Al that 650 ℃ of roasts are handled
2O
3Carrier 100g places cobalt nitrate+magnesium nitrate solution, floods after 2.0 hours to filter, and filter residue forced air drying 5 hours in 105 ℃ of baking ovens obtains catalyst precursor V;
Take by weighing chloroplatinic acid [H respectively
2PtCl
66H
2O] and nickel nitrate [Ni (NO
3)
26H
2O] 1.1g and 15.0g be dissolved in the 200mL distilled water, obtains chloroplatinic acid+nickel nitrate solution; V places chloroplatinic acid+nickel nitrate solution with catalyst precursor, flood after 2.0 hours to filter, and filter residue forced air drying 5 hours in 105 ℃ of baking ovens, roasting 3 hours in 600 ℃ of muffle furnaces again obtains catalyst for decomposing laughing gas V.
Take by weighing the 1g catalyst V, (the v) N that forms 1.35% at 400 ℃, gas volume
2O+1.8% (v) O
2+ 1.01% (v) CO+3.5% (v) CO
2+ 0.02% (v) NO+0.01% (v) NO
2+ 2.5% (v) H
2O+0.03% (v) SO
2Under the experiment condition of+nitrogen, gas volume air speed 2000mL/g.hr, N
2The O rates of decomposing and transforming is 98.9%.
Claims (7)
1, a kind of direct catalyst for decomposing laughing gas is with Al
2O
3Or cordierite is the loaded catalyst of carrier, it is characterized in that: as the activity of such catalysts component, it is characterized in that: constitute the activity of such catalysts component and be divided into major catalyst active constituent and co-catalyst active constituent with one or more metal oxides of IIA, IIB, VIII; Major catalyst active constituent content accounts for 0.01～15.0% (wt) of catalyst, and co-catalyst active constituent content accounts for 0.0～20.0% (wt) of catalyst.
2, according to the described catalyst for decomposing laughing gas of claim 1, it is characterized in that: the metal oxide of preferred Ni and Pt is as the major catalyst active constituent, and active constituent content accounts for 0.01～10.0wt% of catalyst total amount.
3, according to the described catalyst for decomposing laughing gas of claim 1, it is characterized in that: the metal oxide of preferred Co and Mg is as the co-catalyst active constituent, and active constituent content accounts for 0.0～10.0wt% of catalyst total amount.
4, the described catalyst for decomposing laughing gas preparation method of a kind of claim 1～3, the method for employing step impregnation.Wherein used active component Pt adopts the platinum chlorate as the catalyst activity component precursor, and all the other adopt nitrate as the catalyst activity component precursor.
5, by the described catalyst for decomposing laughing gas of claim 1～4, it is characterized in that: when with Al
2O
3During for carrier, carrier needs 600～800 ℃ of preliminary treatment.
6, by the described catalyst for decomposing laughing gas of claim 1～5, it is characterized in that: when being carrier with the cordierite, cordierite pulverizing and screening are obtained 40～60 order particles, the cordierite particle surface needs through Al
2O
3Coating preliminary treatment, and 95～120 ℃ of dryings 3～10 hours, back behind 500～800 ℃ of roasting 2～4h as catalyst carrier.
7, by claim 1,4～6 described catalyst for decomposing laughing gas, it is characterized in that: carrier at first flooded the co-catalyst active constituent after 0.5～12.0 hour, filter, filter residue flooded the major catalyst active constituent 0.1～2.0 hour again 95～120 ℃ of forced air dryings after 3～10 hours, roasting 2～4h under 95～120 ℃ of forced air dryings 3～10 hours, 500～800 ℃ of conditions.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100797249A CN101480615A (en) | 2009-03-10 | 2009-03-10 | Catalyst for decomposing laughing gas and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100797249A CN101480615A (en) | 2009-03-10 | 2009-03-10 | Catalyst for decomposing laughing gas and preparation method thereof |
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451683A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Noble metal catalyst and preparation and application thereof |
| CN102513127A (en) * | 2011-11-21 | 2012-06-27 | 张远洋 | Nitrogen monoxide catalyst with deep ammonia reduction function and preparation method thereof |
| CN105363451A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Efficient catalyst for decomposition of N2O and preparation method and application thereof |
| CN106076112A (en) * | 2016-06-03 | 2016-11-09 | 阳煤集团深州化工有限公司 | One removes N simultaneously2o and NOxmethod |
-
2009
- 2009-03-10 CN CNA2009100797249A patent/CN101480615A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 化学化工大辞典编委会: "《化学化工大辞典》", 31 January 2003 * |
| 陈敬中: "《现代晶体化学-理论与方法》", 31 December 2001 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451683A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Noble metal catalyst and preparation and application thereof |
| CN102513127A (en) * | 2011-11-21 | 2012-06-27 | 张远洋 | Nitrogen monoxide catalyst with deep ammonia reduction function and preparation method thereof |
| CN105363451A (en) * | 2015-12-04 | 2016-03-02 | 中国天辰工程有限公司 | Efficient catalyst for decomposition of N2O and preparation method and application thereof |
| CN105363451B (en) * | 2015-12-04 | 2018-01-26 | 中国天辰工程有限公司 | One kind is used to decompose N2O effective catalyst and its preparation method and application |
| CN106076112A (en) * | 2016-06-03 | 2016-11-09 | 阳煤集团深州化工有限公司 | One removes N simultaneously2o and NOxmethod |
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Application publication date: 20090715 |