CN1203918C - Catalyst with Cu being loaded for taking off waste gas containing HCN and its preparing method as well as application - Google Patents
Catalyst with Cu being loaded for taking off waste gas containing HCN and its preparing method as well as application Download PDFInfo
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- CN1203918C CN1203918C CN 03124259 CN03124259A CN1203918C CN 1203918 C CN1203918 C CN 1203918C CN 03124259 CN03124259 CN 03124259 CN 03124259 A CN03124259 A CN 03124259A CN 1203918 C CN1203918 C CN 1203918C
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Abstract
The present invention relates to a Cu-loaded catalyst for eliminating waste gas containing HCN, and the weight ratio of Cu to Al2O3 of the catalyst is (2.96 to 5.92): 100. The preparation method comprises the steps: Cu (NO3) 2 solution with equal volume is added in a Al2O3 carrier; the catalyst is prepared by impregnating, drying, calcining and reducing by H2. The catalyst prepared is loaded in a reaction furnace, and the furnace temperature rises to 150 to 300 DEG C. Gas mixture containing HCN, NH3, tar oil and air is led into the reaction furnace, and the waste gas is eliminated in a catalytic combustion mode. The present invention has the advantages of simple preparation method, low cost and convenient operation.
Description
Technical field:
The invention belongs to the method for a kind of HCN of removing, relate in particular to a kind of Cu-Al of using
2O
3Remove the method that contains HCN waste gas that produces in the charcoal fiber production process by catalytic oxidation as catalyst.
Background technology:
In the PAN based carbon fiber production process, produce hypertoxic gas HCN, pernicious gas NH inevitably
3Reach waste gas such as tar, if, will certainly cause serious environmental to pollute, even jeopardize vegeto-animal existence without administering directly discharging, especially HCN is the 1mg/kg body weight to people's minimum lethal dose, makes people's adherence in the air of 20ppmHCN hour can cause poisoning.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 four kinds: solution absorption method, absorption method, directly firing method and Production by Catalytic Combustion Process.Absorption process (efforts at environmental protection person's application manual, metallurgical industry publishing house, 1984,456-458) technology comparative maturity, but have secondary pollution.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), stronger to the HCN adsorption capacity, 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 cause part nitrogen to change another kind of pollutant NOx into, moreover to reach and keep high temperature and also need higher energy consumption.And Production by Catalytic Combustion Process is as a kind of novel processing method, because security performance is good, and the purification efficiency height, non-secondary pollution more and more is being subject to people's attention aspect the HCN handling.At present, the catalyst that is used for catalytic combustion is mainly noble metal catalysts such as Pt, Rh, Pd, and its high cost has limited Production by Catalytic Combustion Process in industrial further applying.
Summary of the invention:
The purpose of this invention is to provide a kind of catalyst that removes HCN and preparation method and application of cheapness.
Catalyst weight ratio of the present invention consists of Cu: Al
2O
3=2.96～5.92: 100.
Preparation of catalysts method of the present invention comprises the steps:
(1) with Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 3～6wt%.
(2) at Al
2O
3Add equal-volume Cu (NO in the carrier
3)
2Flood 10～15h under the solution, room temperature.
(3) will be behind 100～150 ℃ of down dry 2～6h, in 450～650 ℃ of roasting 1～4h under air atmosphere, then at 300～650 ℃ of H by the catalyst of (2) preparation
2Reduce 5～8h under the atmosphere, make weight ratio Cu: Al
20
3=2.96～5.92: 100 catalyst.
Application process of the present invention is as follows: the catalyst of above-mentioned preparation is contained in the reacting furnace, furnace temperature is raised to 150-300 ℃ then.To contain HCN, NH
3, tar and Air mixing gas is that 1000-50000/h feeds in the reacting furnace with the air speed, through catalytic combustion waste gas is removed.
Aforesaid Al
2O
3The specification of carrier is 10～100 orders, and specific area is 80～250m
2/ g.
Characteristics of the present invention are:
(1) Cu is loaded on Al
2O
3Go up as catalyst, utilize Al
2O
3Bigger specific area improves the decentralization of Cu, has both given full play to the catalysis advantage of Cu, greatly reduces the cost of catalyst again.
(2) utilize Cu-Al
2O
3Catalyst in air atmosphere under lower temperature 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, NH
3Be oxidized to N
2, H
2O and CO
2Thereby, realize containing removing of HCN waste gas.
(3) initiation temperature is lower, and nitrogenous gas is difficult for changing into another kind of pollutant NOx.Simultaneously, also capable of reducing energy consumption.
(4) utilize tar higher calorific value partly, reduce the supply of heat in the course of reaction, thus also can energy efficient when removing tar.
(5) the present invention prepares simply, and is easy to operate.With pure noble metal catalyst and supporting Pt-Al
2O
3Catalyst is compared, the initiation temperature of this catalyst burning HCN and the decline that production cost all has obvious degree.
The specific embodiment:
Embodiment 1:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 4wt%, then at Al
2O
3(16 orders, specific area 80m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 12h under the solution, room temperature.With the catalyst of preparation at 150 ℃ down behind the dry 5h, in 450 ℃ of roasting 4h under air atmosphere, then at 550 ℃ of H
2Reduce 5h under the atmosphere, make weight ratio Cu: Al
2O
3=3.95: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 150 ℃ then, feed and contain HCN (10ppm), NH
3(50ppm), tar (1vol%), air (5vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 10000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.68ppm (detection method: TJ36-79, i.e. isonicotinic acid-pyrazolone colorimetric method); NH
3Be 16ppm (detection method: TJ36-79, i.e. nessler reagent AAS); Tar class 0.08vol% (detection method: gas chromatography).Do not detect NOx (the Elektron-NOx tester that German Dreager company produces detects).
Embodiment 2:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 6.00w%, then at Al
2O
3(10 orders, specific area 250m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 12h under the solution, room temperature.With the catalyst of preparation at 140 ℃ down behind the dry 1h, in 650 ℃ of roasting 1h under air atmosphere, then at 300 ℃ of H
2Reduce 8h under the atmosphere, make weight ratio Cu: Al
2O
3=5.92: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 300 ℃ then, feed and contain HCN (10vol%), NH
3(10vol%), tar (1vol%), air (50vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 20000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.76ppm; NH
3Be 54ppm; Tar class 0.03vol%.Do not detect NOx.All the other are with embodiment 1.
Embodiment 3:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 5.00wt%, then at Al
2O
3(40 orders, specific area 162m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 10h under the solution, room temperature.With the catalyst of preparation at 100 ℃ down behind the dry 6h, in 500 ℃ of roasting 2h under air atmosphere, then at 300 ℃ of H
2Reduce 8h under the atmosphere, make weight ratio Cu: Al
2O
3=4.94: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 250 ℃ then, feed and contain HCN (1vol%), NH
3(20vol%), tar (5vol vol%), air (40vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 10000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.65ppm; NH
3Be 83ppm; Tar class 0.17vol%.Do not detect NOx.All the other are with embodiment 1.
Embodiment 4:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 3.00wt%, then at Al
2O
3(100 orders, specific area 250m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 15h under the solution, room temperature.With the catalyst of preparation at 100 ℃ down behind the dry 5h, in 550 ℃ of roasting 2h under air atmosphere, then at 500 ℃ of H
2Reduce 6h under the atmosphere, make weight ratio Cu: Al
2O
3=2.96: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 400 ℃ then, feed and contain HCN (1vol%), NH
3(0.50vol%), tar (10vol%), air (50vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 50000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.49ppm; NH
3Be 51ppm; Tar class 0.17vol%.Do not detect NOx.All the other are with embodiment 1.
Embodiment 5:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 5.00wt%, then at Al
2O
3(40 orders, specific area 162m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 13h under the solution, room temperature.With the catalyst of preparation at 120 ℃ down behind the dry 4h, in 600 ℃ of roasting 1h under air atmosphere, then at 500 ℃ of H
2Reduce 6h under the atmosphere, make weight ratio Cu: Al
2O
3=4.94: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 150 ℃ then, feed and contain HCN (200ppm), NH
3(100ppm), tar (5vol%), air (20vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 1000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.35ppm; NH
3Be 29ppm; Tar class 0.14vol%.Do not detect NOx.All the other are with embodiment 1.
Embodiment 6:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 4.00wt%, then at Al
2O
3(100 orders, specific area 250m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 10h under the solution, room temperature.With the catalyst of preparation at 120 ℃ down behind the dry 4h, in 450 ℃ of roasting 3h under air atmosphere, then at 450 ℃ of H
2Reduce 6h under the atmosphere, make weight ratio Cu: Al
2O
3=3.95: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 150 ℃ then, feed and contain HCN (10vol%), NH3 (500ppm), tar (10vol%), air (50vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 10000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.69ppm; NH
3Be 16ppm; Tar class 0.30vol%.Do not detect NOx.All the other are with embodiment 1.
Embodiment 7:
With Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 3.00wt%, then at Al
2O
3(40 orders, specific area 162m
2/ g) add equal-volume Cu (NO in the carrier
3)
2Flood 12h under the solution, room temperature.With the catalyst of preparation at 100 ℃ down behind the dry 6h, in 550 ℃ of roasting 2h under air atmosphere, then at 650 ℃ of H
2Reduce 5h under the atmosphere, make weight ratio Cu: Al
2O
3=2.96: 100 catalyst.The catalyst of preparation is contained in the reacting furnace, furnace temperature is raised to 250 ℃ then, feed and contain HCN (3vol%), NH
3(5vol%), tar (10vol%), air (40vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 15000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.62ppm; NH
3Be 76ppm; Tar class 0.23vol%.Do not detect NOx.All the other are with embodiment 1.
Comparative Examples 1:
Na with 0.5M
2CO
3Solution 100ml absorbs the HCN that contains 100ppm and the NH of 10vol% under room temperature
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 1200m
2The active carbon of/g at room temperature adsorbs the tar of the HCN, the 1vol% that contain 200ppm and the NH of 5vol%
3Mist, measuring the HCN concentration of overflowing is 62ppm, and NH3 is 73ppm, and tar is 0.85vol%.
Comparative Examples 3:
The reactor that does not add any catalyst is heated to 1000 ℃, feeds the tar of the HCN, the 10vol% that contain 500ppm and the NH of 15vol%
3Mist, the air that it is 20vol% that the while blasts above-mentioned mist volume again carries out oxidation, and the residual HCN in reaction back is 1.68ppm, NH
3For 76ppm, tar are 0.01vol%, but also detect simultaneously the NOx of 129ppm.
Comparative Examples 4:
The reacting furnace that netted Pt (95wt%)-Rh (5wt%) catalyst (platinum filament diameter 0.08mm) will be housed is warmed up to 500 ℃, feeds to contain HCN (10ppm), NH
3(10 vol%), tar (10vol%), air (50vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 10000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.83ppm; NH
3Be 92ppm; Tar class 0.45vol%.Do not detect NOx.
Comparative Examples 5:
Pt-Al will be housed
2O
3The reacting furnace of catalyst is warmed up to 350 ℃, feeds to contain HCN (400ppm), NH
3(250ppm), tar (5vol%), air (20vol%) and N
2The gaseous mixture of (as balance gas) etc., the gaseous mixture air speed is 10000/h.Detect the exit concentration of gas at reactor exit: HCN is 1.31ppm; NH
3Be 18ppm; Tar class 0.17vol%.Do not detect NOx.
Claims (4)
1, a kind ofly is used to take off the loaded Cu catalyst that contains HCN waste gas, it is characterized in that weight ratio consists of Cu: Al
2O
3=2.96～5.92: 100.
2. Preparation of catalysts method according to claim 1, this method comprises the steps:
(1) with Cu (NO
3)
23H
2O is dissolved in H
2Among the O, be made into the aqueous solution of 3～6wt%;
(2) at Al
2O
3Add equal-volume Cu (NO in the carrier
3)
2Flood 10～15h under the solution, room temperature;
(3) will be behind 100～150 ℃ of down dry 2～6h, in 450～650 ℃ of roasting 1～4h under air atmosphere, then at 300～650 ℃ of H by the catalyst of (2) preparation
2Reduce 5～8h under the atmosphere, make weight ratio Cu: Al
2O
3=2.96～5.92: 100 catalyst.
3. as Preparation of catalysts method as described in the claim 2, it is characterized in that described Al
2O
3The specification of carrier is 10～100 orders, and specific area is 80～250m
2/ g.
4. Application of Catalyst method according to claim 1 is characterized in that comprising the steps:
Catalyst is contained in the reacting furnace, furnace temperature is raised to 150-300 ℃ then, will contain HCN, NH
3, tar and Air mixing gas is that 1000-50000/h feeds in the reacting furnace with the air speed, through catalytic combustion waste gas is removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03124259 CN1203918C (en) | 2003-04-30 | 2003-04-30 | Catalyst with Cu being loaded for taking off waste gas containing HCN and its preparing method as well as application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03124259 CN1203918C (en) | 2003-04-30 | 2003-04-30 | Catalyst with Cu being loaded for taking off waste gas containing HCN and its preparing method as well as application |
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| Publication Number | Publication Date |
|---|---|
| CN1462652A CN1462652A (en) | 2003-12-24 |
| CN1203918C true CN1203918C (en) | 2005-06-01 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| CN101475170B (en) * | 2009-01-15 | 2010-10-13 | 华烁科技股份有限公司 | Method for removing HCN in CO2 raw gas |
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| CN103185344B (en) * | 2012-12-13 | 2015-08-19 | 浙江海洋学院 | Utilize the technique of useless hydrogenation catalyst process organic exhaust gas |
| CN106881088A (en) * | 2015-12-15 | 2017-06-23 | 南京源泉环保科技股份有限公司 | A kind of air oxidation broken cyanide catalyst and preparation method thereof |
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| CN111228980B (en) * | 2020-03-10 | 2020-11-24 | 昆明理工大学 | Method for combined removal of phosphorus, sulfur, cyanogen and nitrogen oxide in waste gas |
| CN111592903B (en) * | 2020-04-29 | 2021-10-19 | 中国科学院广州能源研究所 | Method for removing tar by using municipal sludge |
| CN114011408A (en) * | 2021-09-23 | 2022-02-08 | 北京化工大学 | Process method for treating carbon fiber production process waste gas by using molecular sieve catalyst |
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2003
- 2003-04-30 CN CN 03124259 patent/CN1203918C/en not_active Expired - Fee Related
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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|---|---|
| CN1462652A (en) | 2003-12-24 |
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