CN1176737C - Method for removing waste gas containing HCN by platinum-rhodium-palladium catalyst - Google Patents
Method for removing waste gas containing HCN by platinum-rhodium-palladium catalyst Download PDFInfo
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- CN1176737C CN1176737C CNB021313024A CN02131302A CN1176737C CN 1176737 C CN1176737 C CN 1176737C CN B021313024 A CNB021313024 A CN B021313024A CN 02131302 A CN02131302 A CN 02131302A CN 1176737 C CN1176737 C CN 1176737C
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- hcn
- rhodium
- platinum
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- tar
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Abstract
The present invention relates to an application method for eliminating waste gas containing HCN, which takes platinum-rhodium-palladium as catalyst and adopts a catalytic oxidation method. The method comprises the following steps: loading platinum-rhodium-palladium catalyst in a reaction furnace, and then rising the furnace temperature to 250 to 450 DEG C; afterwards, leading N2 containing HCN, NH3, tar oil, etc. into the reaction furnace and simultaneously leading air (the volume of the air is 5% to 50% of the total gases) into the reaction furnace in order to eliminate hypertoxic and harmful gases by a catalytic oxidation method. The present invention has the advantages of simple preparation and easy operation, the temperature used is lower, and gases containing nitrogen are difficultly changed into another contaminant NO<x>. In addition, energy consumption can also be reduced. In the eliminating process, higher heat value of the tar oil part can be used for reducing heat supply in the process of reaction, so when the tar oil is eliminated, the energy consumption can be reduced simultaneously.
Description
Affiliated field
The invention belongs to the method for a kind of HCN of removing, relate in particular to and a kind ofly remove the method that contains HCN waste gas by catalytic oxidation with platinum rhodium palladium.
Background technology:
PAN based carbon fiber produces inevitably and contains hypertoxic gas HCN, pernicious gas NH in process of production
3Reach waste gas such as tar, if, will certainly cause environmental pollution seriously without administering directly discharging, even jeopardize vegeto-animal existence, especially the hypertoxicity of HCN makes people's adherence in the air of 20ppmHCN hour can cause poisoning, is the 1mg/kg body weight to people's lethal dose.Therefore, removing of research HCN is extremely important with preserving the ecological environment to development charcoal fiber industry.
At present, the method that removes HCN mainly contains three kinds: solution absorption method, absorption method and firing method.Absorption process (efforts at environmental protection person's application manual, metallurgical industry publishing house, 1984, mainly be to use Na 456-458)
2CO
3Solution absorbs HCN, adds iron ion and CN again
-Reaction generates potassium ferrocyanide, but because this method is handled not thoroughly, makes the HCN can not qualified discharge; Another kind of absorption process is an alkaline chlorination process, and this method was divided into for two stages carries out, and the phase I adds alkali, adds oxychloride under the condition of pH＞10, and second stage adds acid, and to adjust pH value be 7.5-8, adds oxychloride again.Though this method is to use more general method, only is suitable for handling and contains the less waste water of cyanogen amount.Absorption method (carbon, 1991,29 (7), 887-892; J.colloid and interface science, 1987,116 (1), be to adopt absorption HCN such as adsorbent such as active carbon, silica gel and metal 211-220), wherein the HCN adsorption capacity is stronger, but adsorption capacity is limited.Said method also exists can not remove NH
3Problem with tar.The burning rule is that HCN is descended and O at high temperature (＞900 ℃)
2React, make the HCN oxidation generate H
2O, CO
2, N
2And innoxious, but owing to need higher temperature to cause part nitrogen to change N into
2The time also generated another kind of pollutant NO
x, moreover will reach and keep high temperature and also need higher energy consumption.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly remove the method for HCN as catalyst by catalytic oxidation with platinum rhodium palladium, this method can remove NH when removing HCN
3And tar, and non-secondary pollution.
It is as follows that platinum-rhodium-palladium catalyst of the present invention adopts catalytic oxidation to remove the method that contains HCN waste gas:
(1) earlier platinum-rhodium-palladium catalyst is contained in the reacting furnace, furnace temperature is raised to 250-450 ℃ then;
(2) air speed is 5000-30000h
-1Contain HCN, NH
3Feed in the reacting furnace with the waste gas of tar, the while bubbling air, its volume accounts for the 5%-50% of cumulative volume.
The ratio of aforesaid platinum-rhodium-palladium catalyst is Pt:90-98wt%Rh:1-5wt%Pd:1-5wt%.
Aforesaid platinum-rhodium-palladium catalyst is that platinum rhodium palladium filament diameter is that the netted or particle diameter of 0.07-0.09mm is the graininess of 0.5mm-5mm.
HCN concentration is in the aforesaid waste gas: 10ppm-10%, NH
3Concentration is: 50ppm-20%, tar-concentration is: 1vol%-10vol%.
Characteristics of the present invention are:
(1) utilize platinum-rhodium-palladium catalyst in air atmosphere in lower temperature as being lower than under 450 ℃ to HCN, NH
3Carry out oxidation with gases (being designated hereinafter simply as the waste gas that contains HCN) such as tar, make HCN be oxidized to harmless H
2O, CO
2, N
2, the material of tar one class is oxidized to CO
2And H
2O, and NH
3Also can be oxidized to N respectively
2, H
2O, thus realize that containing HCN waste gas removes.
(2) temperature of Shi Yonging is lower, and nitrogenous gas is difficult for changing into another kind of pollutant NO
xIn addition, also capable of reducing energy consumption.
(3) utilize tar higher calorific value partly, reduce the supply of heat in the course of reaction, thus also can energy efficient when removing tar.
(4) preparation is simple, easy to operate.
The specific embodiment;
Embodiment 1: the reacting furnace that netted Pt (90wt%)-Rh (5wt%)-Pd (5wt%) catalyst (platinum rhodium palladium filament diameter 0.07mm) will be housed is warmed up to 250 ℃, and the feeding air speed is 15000h
-1The waste gas that contains HCN (10ppm), NH3 (50ppm), tar (1vol%), bubbling air simultaneously, its volume accounts for 5% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.62ppm (detection method: TJ36-79, i.e. isonicotinic acid-pyrazolone colorimetric method); NH
3Be 11ppm (detection method: TJ36-79, i.e. nessler reagent AAS); Tar class 0.017% (detection method: gas chromatography).Do not detect NO
x(the Elektron-NOx tester that German Dreager company produces detects).
Embodiment 2: the reacting furnace that netted Pt (90wt%)-Rh (5wt%)-Pd (5wt%) catalyst (platinum rhodium palladium filament diameter 0.09mm) will be housed is warmed up to 450 ℃, and the feeding air speed is 10000h
-1Contain HCN (10%), NH
3(10%), the waste gas of tar (1vol%), bubbling air simultaneously, its volume accounts for 50% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.58ppm; NH
3Be 55ppm; Tar class 0.004%.Do not detect NO
xAll the other are with embodiment 1.
Embodiment 3: the reacting furnace that netted Pt (98wt%)-Rh (1wt%)-Pd (1wt%) catalyst (platinum filament diameter 0.07mm) will be housed is warmed up to 450 ℃, and the feeding air speed is 30000h
-1Contain HCN (10ppm), NH
3(50ppm), the waste gas of tar (1%), bubbling air simultaneously, its volume accounts for 50% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.57ppm; NH
3Be 22ppm; Tar class 0.03%.Do not detect NO
xAll the other are with embodiment 1.
Embodiment 4: the reacting furnace that netted Pt (98wt%)-Rh (1wt%)-Pd (1wt%) catalyst (platinum filament diameter 0.08mm) will be housed is warmed up to 350 ℃, and the feeding air speed is 5000h
-1Contain HCN (1%), NH
3(0.5%), the waste gas of tar (10%), bubbling air simultaneously, its volume accounts for 50% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.68ppm; NH
3Be 53ppm; Tar class 0.09%.Do not detect NO
xAll the other are with embodiment 1.
Embodiment 5: the reacting furnace that graininess Pt (90wt%)-Rh (5wt%)-Pd (5wt%) catalyst (5mm) will be housed is warmed up to 450 ℃, and the feeding air speed is 10000h
-1Contain HCN (50ppm), NH
3(20vol%), the waste gas of tar (1vol%), bubbling air simultaneously, its volume accounts for 40% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.80ppm; NH
3Be 77ppm; Tar class 0.01%.Do not detect NO
xAll the other are with embodiment 1.
Embodiment 6: the reacting furnace that graininess Pt (90wt%)-Rh (5wt%)-Pd (5wt%) catalyst (0.5mm) will be housed is warmed up to 250 ℃, and the feeding air speed is 20000h
-1Contain HCN (10ppm), NH
3(10vol%), the waste gas of tar (1vol%), bubbling air simultaneously, its volume accounts for 25% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.23ppm; NH
3Be 51ppm; The tar class is 0.1%.Do not detect NO
xAll the other are with embodiment 1.
Embodiment 7: the reacting furnace that graininess Pt (90wt%)-Rh (5wt%)-Pd (5wt%) catalyst (3mm) will be housed is warmed up to 450 ℃, and the feeding air speed is 8000h
-1Contain HCN (10%), NH
3(50ppm), the waste gas of tar (10vol%), bubbling air simultaneously, its volume accounts for 50% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.61ppm; NH
3Be 9ppm; The tar class is 0.18%.Do not detect NO
xAll the other together
Embodiment 1.
Embodiment 8: the reacting furnace that graininess Pt (98wt%)-Rh (1wt%)-Pd (1wt%) catalyst (5mm) will be housed is warmed up to 350 ℃, and the feeding air speed is 30000h
-1Contain HCN (0.1%), NH
3(1%), the waste gas of tar (5vol%), bubbling air simultaneously, its volume accounts for 30% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.91ppm; NH
3Be 57ppm; The tar class is 0.41%.Do not detect NO
xAll the other are with embodiment 1.
Embodiment 9: the reacting furnace that graininess Pt (98wt%)-Rh (1wt%)-Pd (1wt%) catalyst (5mm) will be housed is warmed up to 250 ℃, and the feeding air speed is 500h
-1Contain HCN (10ppm), NH
3(50ppm), the waste gas of tar (1vol%), bubbling air simultaneously, its volume accounts for 5% of cumulative volume.Detect the exit concentration of gas at reactor exit: HCN is 1.71ppm; NH
3Be 22ppm; The tar class is 0.1%.Do not detect NO
xAll the other are with embodiment 1.
Comparative Examples 1: with the Na of 0.5M
2CO
3Solution 100ml absorbs air speed under room temperature be 15000h
-1The HCN that contains 100ppm and the NH of 10vol%
3Mist adds iron ion and CN again
-Reaction generates potassium ferrocyanide, and measuring the HCN concentration of overflowing is 23ppm, NH
3Be 513ppm, high like this concentration can not qualified discharge.
Comparative Examples 2: with the 1g specific area is that at room temperature to adsorb air speed be 10000h for the active carbon of 1200m2/g
-1The HCN that contains 200ppm, 1% tar and the NH of 5vol%
3Mist, measuring the HCN concentration of overflowing is 62ppm, NH
3Be 73ppm, tar is 0.85%.
Comparative Examples 3: the reactor that does not add any catalyst is heated to 1000 ℃, and the feeding air speed is 5000h
-1The tar of the HCN that contains 500ppm, 10vol% and the NH of 15vol%
3Mist blasts simultaneously above-mentioned mist volume again and is 20% air and carries out oxidation, and the residual HCN in reaction back is 1.68ppm, NH
3For 76ppm, tar are 0.01%, but also detect simultaneously the NO of 129ppm
x
Claims (3)
1, a kind of method of removing waste gas containing HCN by platinum-rhodium-palladium catalyst is characterized in that comprising the steps:
(1) earlier is that the platinum-rhodium-palladium catalyst of Pt:90-98wt%Rh:1-5wt%Pd:1-5wt% is contained in the reacting furnace, furnace temperature is raised to 250-450 ℃ then ratio;
(2) air speed is in the waste gas feeding reacting furnace that contains HCN, NH3 and tar of 5000-30000h-1, the while bubbling air, and its volume accounts for the 5%-50% of cumulative volume.
2, the method for a kind of removing waste gas containing HCN by platinum-rhodium-palladium catalyst as claimed in claim 1 is characterized in that described platinum-rhodium-palladium catalyst is that platinum rhodium palladium filament diameter is the netted catalyst of 0.07-0.09mm.
3, the method for a kind of removing waste gas containing HCN by platinum-rhodium-palladium catalyst as claimed in claim 1 is characterized in that described platinum-rhodium-palladium catalyst is that particle diameter is the pellet type catalyst of 0.5mm-5mm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021313024A CN1176737C (en) | 2002-09-27 | 2002-09-27 | Method for removing waste gas containing HCN by platinum-rhodium-palladium catalyst |
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|---|---|---|---|
| CNB021313024A CN1176737C (en) | 2002-09-27 | 2002-09-27 | Method for removing waste gas containing HCN by platinum-rhodium-palladium catalyst |
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| CN1176737C true CN1176737C (en) | 2004-11-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269297B (en) * | 2008-05-21 | 2011-09-14 | 昆明理工大学 | Catalytic oxidation purification method for hydrogen cyanide in industrial waste gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101491747B (en) * | 2008-12-10 | 2011-04-20 | 上海泰禾(集团)有限公司 | Method for processing waste gas generated in isophthalonitrile production process |
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2002
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269297B (en) * | 2008-05-21 | 2011-09-14 | 昆明理工大学 | Catalytic oxidation purification method for hydrogen cyanide in industrial waste gas |
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