CN107913708A - HCN-containing gases catalyst for catalytic oxidation and preparation method thereof - Google Patents
HCN-containing gases catalyst for catalytic oxidation and preparation method thereof Download PDFInfo
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- CN107913708A CN107913708A CN201610881458.1A CN201610881458A CN107913708A CN 107913708 A CN107913708 A CN 107913708A CN 201610881458 A CN201610881458 A CN 201610881458A CN 107913708 A CN107913708 A CN 107913708A
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- containing gases
- catalytic oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 239000007789 gas Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000007255 decyanation reaction Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 36
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 55
- 239000010949 copper Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 19
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 13
- 206010013786 Dry skin Diseases 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- -1 Alkene nitrile Chemical class 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IIHRCAVVTRFILY-UHFFFAOYSA-N [O].N#CC#N Chemical compound [O].N#CC#N IIHRCAVVTRFILY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to HCN-containing gases catalyst for catalytic oxidation and preparation method thereof.To solve the problems, such as that existing catalyst reaction efficiency is low.The present invention is by using HCN-containing gases catalyst for catalytic oxidation, in parts by weight, including following components：(1) 90~99.5 part of catalyst carrier；The technical solution of (2) 0.1~5 parts of rutheniums, preferably solves the problems, such as this, the removing available for cyanide in HCN-containing gases.
Description
Technical field
The present invention relates to HCN-containing gases catalyst for catalytic oxidation and preparation method thereof.
Technical background
HCN-containing gases refer mainly to the organic exhaust gas containing hydrogen cyanide, acetonitrile and acrylonitrile etc., are a kind of harm biology health
Hypertoxic pollutant.At present, decyanating method mainly includes the technologies such as absorption and sorption, burning, catalysis oxidation and hydrolysis.Due to catalysis
Efficiency is high, and decyanation effect is good, has received widespread attention.Catalytic oxidation by reaction process can be divided into two-step method and
One-step method.Two-step method refers to HCN-containing gases first are oxidized to carbon dioxide, nitrogen oxides and water, then by denitrating catalyst by nitrogen
Oxide changes into harmless nitrogen.One-step technology technical economic benefit is obvious, and process route is simpler, in catalyst
Under effect, HCN-containing gases are directly translated into carbon dioxide, water and nitrogen.
CN102734812 disclosure of the invention is a kind of to be used for removing HCN-containing gases method, is situated between using transition metal support type
Pore zeolite catalyst carries out removing catalytic reaction to HCN-containing gases.Wherein mesopore molecular sieve carrier is：MCM-41、MCM-48、
SBA-15, SBA-16, KIT-5 or KIT-6, transition metal active component are：One kind or several in Cu, Co, Cr, Mn, Ag or V
Kind, the mass ratio 1: 0.02~0.07 of carrier and transition metal component, by molecular sieve catalyst, is placed in fixed-bed quartz reactor
In, under normal pressure, reacting furnace temperature is raised to 350 DEG C~650 DEG C, by the gaseous mixture of HCN-containing gases, oxygen and nitrogen with air speed
17000~24000h-1It is passed through in reacting furnace, removes exhaust gas through catalysis burning.This method removal efficiency is low.
CN1404904 discloses a kind of method of removing waste gas containing HCN by platinum-rhodium catalyst, by platinum-rhodium catalyst mounted in reaction
In stove, furnace temperature is then raised to 250~550 DEG C；Contain HCN, NH3Exhaust gas with tar is with 5000~30000h-1Air speed lead to
Enter in reacting furnace, while be passed through air, its volume of the total volume 5%~50%.The temperature that the invention uses is relatively low, nitrogenous
Gas is not easy to be changed into another pollutant NO2.But this method catalyst cost is higher.
CN101362051 discloses a kind of acrylonitrile device tail-gas treatment technique, suitable for the third of acrylonitrile installation discharge
Alkene nitrile exhaust gas, it is characterised in that acrylonitrile off-gas mixes after gas-liquid separator separates free water with air, with noble metal honeycomb
Catalyst makees catalyst, carries out catalytic oxidation, and harmful volatile organic matter is converted into carbon dioxide and water；Again with choosing
Selecting property reduction honeycomb catalyst makees catalyst, and ammonia the making choice property catalytic reduction reaction added, by the nitrogen oxidation in tail gas
Thing is reduced into nitrogen and water.This method is complicated, and need to add ammonia, and material consumption is high.
The content of the invention
The first technical problem to be solved by the present invention is the cyanogen in catalytic oxidative desulfurization HCN-containing gases of the prior art
The problem of compound efficiency is low, there is provided a kind of new catalyst for catalytic oxidation, the catalyst have efficient excellent of removing cyanide
Point.
The second technical problem to be solved by the present invention is the preparation side with catalyst described in one of above-mentioned technical problem
Method.
The third technical problem to be solved by the present invention is giving up containing cyanogen using one of the above-mentioned technical problem catalyst
The catalytic oxidation technologies of gas.
To solve one of above-mentioned technical problem, technical scheme is as follows：
HCN-containing gases catalyst for catalytic oxidation, in parts by weight, including following components：
(1) 90~99.5 part of catalyst carrier；
(2) 0.1~5 parts of rutheniums.
In above-mentioned technical proposal, the catalyst preferably further includes (3) 0.1~5 parts of copper, and ruthenium is with copper in removing HCN-containing gases
In cyanogen effect in terms of both there is obvious cooperative effect.
In above-mentioned technical proposal, the catalyst carrier preferably is selected from TiO2、ZrO2、SiO2And Al2O3In one kind.
In above-mentioned technical proposal, the catalyst shape is preferably honeycomb type, trifolium-shaped, column or spherical.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
The preparation method of catalyst any one of the technical solution of one of above-mentioned technical problem, including：
(1) solution of the compound containing ruthenium element is mixed with carrier；
(2) roast.
In above-mentioned technical proposal, when containing copper in the catalyst, the preparation method can be further to include
The method one of following steps：
(1) mixed solution of the compound containing ruthenium element and the compound containing copper is mixed with carrier；
(2) roast.
In above-mentioned technical proposal, when containing copper in the catalyst, the preparation method can be further to include
The method two of following steps：
1) solution of the compound containing ruthenium element is mixed with carrier；
2) roasting obtains catalyst precarsor I；
3) compound solution containing copper is mixed with precursor I；
4) roast.
In above-mentioned technical proposal, when containing copper in the catalyst, the preparation method can be further to include
The method three of following steps：
I) compound solution containing copper is mixed with carrier；
Ii) roasting obtains catalyst precarsor II；
Iii) solution of the compound containing ruthenium element is mixed with catalyst precarsor II；
Iv) roast.
It has been surprisingly found that had using catalyst made from the above method two in terms of the cyanogen in removing HCN-containing gases
The effect more prominent compared with other two methods.
In above-mentioned technical proposal, calcination temperature is preferably 300~700 DEG C.
In above-mentioned technical proposal, when roasting time is preferably 1~6 small.
In above-mentioned technical proposal, the atmosphere of roasting is preferably inert atmosphere or oxidizing atmosphere.
In above-mentioned technical proposal, the oxidizing atmosphere is preferably air.
In above-mentioned technical proposal, the compound containing ruthenium element preferably is selected from any one in nitric acid ruthenium, ruthenic chloride and ruthenium acetate
Kind.
In above-mentioned technical proposal, the compound containing copper preferably is selected from copper nitrate, copper chloride, copper sulphate and copper acetate
Any one.
To solve the three of above-mentioned technical problem, technical scheme is as follows：
Catalyst any one of the technical solution of one of above-mentioned technical problem is in HCN-containing gases catalysis oxidation decyanation
Application.
Specifically application process can be：In the presence of above-mentioned catalyst, by the HCN-containing gases and oxygenous oxidation
The cyanide removed in exhaust gas is reacted in agent in the reactor.
In above-mentioned technical proposal, the oxidant is preferably air or oxygen-enriched.
In above-mentioned technical proposal, the temperature of reaction is preferably 280~500 DEG C.
In above-mentioned technical proposal, total volume space velocity of HCN-containing gases and oxidant is preferably 1000~30000h-1。
In above-mentioned technical proposal, the reactor is preferably fixed bed reactors.
In above-mentioned technical proposal, the species of cyanogen in HCN-containing gases is not limited, as long as it is equal containing CN groups in molecule
Effect with removing, such as, but not limited to dicyanogen ((CN)2), sulphur cyanogen ((SCN)2), oxygen cyanogen ((OCN)2)、HCN、HSCN、
The saturated nitriles (such as, but not limited to acetonitrile) of HOCN, C2~C10, C3~C10 unsaturated nitrile (such as, but not limited to acrylonitrile,
Methacrylonitrile, benzonitrile, two benzonitrile) etc..
One skilled in the art will appreciate that mechanical strength higher can be obtained if be dried in advance before firing
Catalyst, from this angle, recommends dry step before firing.Dry actual temp does not limit, such as but
60~120 DEG C are not limited to, further non-limiting example can be：70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C etc..
Technical solution using the present invention, the results showed that the C-06 catalyst containing ruthenium and copper while preparation with the present invention,
It is 380 DEG C in reaction temperature, air speed 12000h-1, the cyanide in HCN-containing gases can be effectively removed, after catalytic oxidation treatment,
Acrylonitrile in HCN-containing gases is down to 0.8ppm from 1,925ppm；Hydrogen cyanide is down to 1.2ppm from 240ppm, NOx content in tail gas
For 17.4ppm, preferable technique effect is achieved.
Below by embodiment, the invention will be further elaborated, but these embodiments are not anyway to this hair
Bright scope is construed as limiting.
Embodiment
【Embodiment 1】
1st, catalyst preparation
In terms of weight proportion, ZrO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-01.
By 96 parts of ZrO2Catalyst carrier is impregnated in equivalent to the RuCl containing 0.2 part of Ru at room temperature3With the Cu of 3.8 parts of Cu
(NO3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst A-01 is obtained.Catalyst
Formula be shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-01 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 2】
1st, catalyst preparation
In terms of weight proportion, SiO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-02.
By 96 parts of SiO2Catalyst carrier is impregnated in equivalent to the RuCl containing 0.2 part of Ru at room temperature3With the Cu of 3.8 parts of Cu
(NO3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst A-02 is obtained.Catalyst
Formula be shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-02 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 3】
1st, catalyst preparation
In terms of weight proportion, Al2O3:Ru:Cu is 96:0.2:3.8 prepare catalyst A-03.
By 96 parts of Al2O3Catalyst carrier is impregnated in equivalent to the RuCl containing 0.2 part of Ru at room temperature3With the Cu of 3.8 parts of Cu
(NO3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst A-03 is obtained.Catalyst
Formula be shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-03 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 4】
1st, catalyst preparation
In terms of weight proportion, TiO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-04.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the RuCl containing 0.2 part of Ru at room temperature3With the Cu of 3.8 parts of Cu
(NO3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst A-04 is obtained.Catalyst
Formula be shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-04 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 5】
1st, catalyst preparation
In terms of weight proportion, TiO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-05.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the Ru (NO containing 0.2 part of Ru at room temperature3)3With the Cu of 3.8 parts of Cu
(NO3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst A-05 is obtained.Catalyst
Formula be shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-05 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 6】
1st, catalyst preparation
In terms of weight proportion, TiO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-06.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the Ru (NO containing 0.2 part of Ru at room temperature3)3In aqueous solution overnight,
When roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst precursor B-06 is obtained.By B-06 be impregnated in equivalent to
Cu (NO containing 3.8 parts of Cu3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, it is catalyzed
Agent A-06.The formula of catalyst is shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-06 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 7】
1st, catalyst preparation
In terms of weight proportion, TiO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-07.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the Cu (NO containing 3.8 parts of Cu at room temperature3)2In aqueous solution overnight,
When roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst precursor B-07 is obtained.By B-07 be impregnated in equivalent to
Ru (NO containing 0.2 part of Ru3)3In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, it is catalyzed
Agent A-07.The formula of catalyst is shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-07 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Embodiment 8】
1st, catalyst preparation
In terms of weight proportion, TiO2:Ru:Cu is 96:0.2:3.8 prepare catalyst A-08.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the Ru (NO containing 0.4 part of Ru at room temperature3)3In aqueous solution overnight,
When roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, catalyst precursor B-08 is obtained.By B-08 be impregnated in equivalent to
Cu (NO containing 3.6 parts of Cu3)2In aqueous solution overnight, when roasting 4 is small under 400 DEG C of air atmospheres after 80 DEG C of dryings, it is catalyzed
Agent A-08.The formula of catalyst is shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of A-08 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Comparative example 1】
1st, catalyst preparation
In terms of weight proportion, TiO2:Ru is 96:4 prepare catalyst D-01.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the Ru (NO containing 4 parts of Ru at room temperature3)3In aqueous solution overnight, 80
When roasting 4 is small under 400 DEG C of air atmospheres after DEG C dry, catalyst D-01 is obtained.The formula of catalyst is shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of D-01 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
【Comparative example 2】
1st, catalyst preparation
In terms of weight proportion, TiO2:Cu is 96:4 prepare catalyst D-02.
By 96 parts of TiO2Catalyst carrier is impregnated in equivalent to the Cu (NO containing 4 parts of Cu at room temperature3)2In aqueous solution overnight, 80
When roasting 4 is small under 400 DEG C of air atmospheres after DEG C dry, catalyst D-02 is obtained.The formula of catalyst is shown in Table 1.
2nd, evaluating catalyst
HCN-containing gases (acrylonitrile 1925ppm, hydrogen cyanide 240ppm) press 1 with air：After 5 mixing, by being filled with 800mL
The fixed bed reactors of D-02 catalyst.Reaction temperature in reactor is 380 DEG C, reaction velocity 12000h-1.Reaction result is shown in
Table 2.
The formula of 1. catalyst of table
| Embodiment | Catalyst | Catalyst formulation | Each component quality proportioning |
| Embodiment 1 | A-01 | ZrO2:Ru:Cu | 96:0.2:3.8 |
| Embodiment 2 | A-02 | SiO2:Ru:Cu | 96:0.2:3.8 |
| Embodiment 3 | A-03 | Al2O3:Ru:Cu | 96:0.2:3.8 |
| Embodiment 4 | A-04 | TiO2:Ru:Cu | 96:0.2:3.8 |
| Embodiment 5 | A-05 | TiO2:Ru:Cu | 96:0.2:3.8 |
| Embodiment 6 | A-06 | TiO2:Ru:Cu | 96:0.2:3.8 |
| Embodiment 7 | A-07 | TiO2:Ru:Cu | 96:0.2:3.8 |
| Embodiment 8 | A-08 | TiO2:Ru:Cu | 96:0.4:3.6 |
| Comparative example 1 | D-01 | TiO2:Ru | 96:4 |
| Comparative example 2 | D-02 | TiO2:Cu | 96:4 |
2. reaction result of table
Claims (10)
1. HCN-containing gases catalyst for catalytic oxidation, in parts by weight, including following components：
(1) 90~99.5 part of catalyst carrier；
(2) 0.1~5 parts of rutheniums.
2. catalyst for catalytic oxidation according to claim 1, it is characterized in that the catalyst carrier is selected from TiO2、ZrO2、
SiO2And Al2O3In one kind.
3. catalyst for catalytic oxidation according to claim 1, it is characterized in that the catalyst shape is honeycomb type, three leaves
Careless type, column or spherical.
4. the preparation method of catalyst any one of claims 1 to 3, including：
(1) solution of the compound containing ruthenium element is mixed with carrier；
(2) roast.
5. preparation method according to claim 4, it is characterized in that calcination temperature is 300~700 DEG C.
6. preparation method according to claim 4, it is characterized in that when roasting time is 1~6 small.
7. preparation method according to claim 4, it is characterized in that the atmosphere of roasting is inert atmosphere or oxidizing atmosphere.
8. preparation method according to claim 7, it is characterized in that the oxidizing atmosphere is air.
9. preparation method according to claim 4, it is characterized in that the compound containing ruthenium element be selected from nitric acid ruthenium, ruthenic chloride and
Any one in ruthenium acetate.
10. application of the catalyst any one of claims 1 to 3 in HCN-containing gases catalysis oxidation decyanation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110639500A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Combustion catalyst for cyanogen-containing waste gas and application of combustion catalyst in cyanogen-containing waste gas treatment |
| CN110639508A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for wet oxidation of organic amine industrial wastewater and application thereof |
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| CN1816608A (en) * | 2003-06-06 | 2006-08-09 | 恩格哈德公司 | Catalyst additives for the removal of nh3 and hcn in the regeneration zone during catalytic cracking process |
| CN102734812A (en) * | 2011-04-14 | 2012-10-17 | 北京化工大学 | Method for removing cyanogens-containing waste gas |
| CN103638943A (en) * | 2013-10-15 | 2014-03-19 | 河南省科学院能源研究所有限公司 | Cobalt-based Fischer-Tropsch fixed bed catalyst used for biomass synthetic gas and preparation method therefor |
| CN104353459A (en) * | 2014-11-11 | 2015-02-18 | 中国科学院过程工程研究所 | Supported bimetallic catalyst for catalytic oxidation of VOCs and preparation method and application thereof |
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| CN1816608A (en) * | 2003-06-06 | 2006-08-09 | 恩格哈德公司 | Catalyst additives for the removal of nh3 and hcn in the regeneration zone during catalytic cracking process |
| CN102734812A (en) * | 2011-04-14 | 2012-10-17 | 北京化工大学 | Method for removing cyanogens-containing waste gas |
| CN103638943A (en) * | 2013-10-15 | 2014-03-19 | 河南省科学院能源研究所有限公司 | Cobalt-based Fischer-Tropsch fixed bed catalyst used for biomass synthetic gas and preparation method therefor |
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| CN110639500A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Combustion catalyst for cyanogen-containing waste gas and application of combustion catalyst in cyanogen-containing waste gas treatment |
| CN110639508A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for wet oxidation of organic amine industrial wastewater and application thereof |
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