CN107913594A - The removal methods of HCN-containing gases - Google Patents
The removal methods of HCN-containing gases Download PDFInfo
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Abstract
The present invention relates to the removal methods of HCN-containing gases.To solve the problems, such as that HCN-containing gases are high with NOx content in the tail gas after existing catalyst treatment.The present invention in the presence of a catalyst, makes HCN-containing gases and oxygenous oxidant reacts the cyanide removed in exhaust gas in the reactor, the catalyst by using the removal methods of HCN-containing gases, in parts by weight, including following components：(1) 10~90 part of catalyst carrier；The technical solution of (2) 0.1~20 parts of cupric oxide, preferably solves the problems, such as this, the removing available for cyanide in HCN-containing gases.
Description
Technical field
The present invention relates to the removal methods of HCN-containing gases.
Technical background
Industrial HCN-containing gases primary pollution source comes from coke-oven plant, cyanide factory, Electroplate Factory and carbon fiber production process
Such exhaust gas is a kind of hypertoxic pollutant for endangering biology health, it is necessary to pass through stringent processing, after testing after qualification, and Fang Kepai
Put.At present, in China's cyanide discharge new standard, acrylonitrile content need to be less than 0.5mg/m3, and hydrogen cyanide is less than 1.9mg/m3.It is de-
Cyanogen method mainly includes the technologies such as absorption and sorption, burning, catalysis oxidation and hydrolysis.Catalytic oxidation is organic as a kind of processing
The effective ways of exhaust gas, have initiation temperature is low, non-secondary pollution, waste heat can reuse, convenient operation and management, running expense it is low etc.
Advantage, therefore there is unique advantage in terms of tail gas is handled, it is a kind of up-and-coming method.
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.
CN1416950 discloses a kind of preparation method for the catalyst for being used to remove the exhaust gas containing HCN.By H2PtCl6It is dissolved in
H2In O, then in Al2O3Isometric H is added in carrier2PtCl6Solution dipping, dry, roasting, reduction.It is being filled with the catalysis
In the reacting furnace of agent dress, furnace temperature is raised to 250~450 DEG C, HCN, NH will be contained3, tar and air gaseous mixture be passed through reaction
In stove, exhaust gas is removed through catalysis burning.But catalyst cost is higher in this method.
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 of carrier and transition metal component:0.02~0.07, by molecular sieve catalyst, it 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.
The content of the invention
The technical problems to be solved by the invention are to solve HCN-containing gases with the tail gas after existing catalyst treatment
The problem of NOx content is high, there is provided a kind of removal methods of new HCN-containing gases, the removal methods have removing cyanide excellent in efficiency
And remove the advantages of NOx content is low in the tail gas after cyanide.
In order to solve the above technical problems, technical scheme is as follows：
The removal methods of HCN-containing gases, in the presence of a catalyst, are reacting HCN-containing gases and oxygenous oxidant
Reaction removes the cyanide in exhaust gas in device, in parts by weight, including following components：
(1) 10~90 part of catalyst carrier；
(2) 0.1~20 parts of cupric oxide.
In above-mentioned technical proposal, the carrier is not particularly limited, and such as, but not limited to the catalyst carrier is selected from
TiO2、ZrO2、SiO2And Al2O3In one kind.
In above-mentioned technical proposal, the geometry of the catalyst is not particularly limited, such as, but not limited to honeycomb type, three
Leaf grass type, column or spherical.
In above-mentioned technical proposal, the catalyst further preferably includes (3) 0.1~70 parts of tungsten oxides, cupric oxide and tungsten oxides
There is cooperative effect in terms of NOx generation amount is reduced.
In above-mentioned technical proposal, the tungsten oxide of any crystalline form can, but preferably hexagonal phase tungsten oxide nano.Hexagonal phase
The commercially available channel of tungsten oxide nano obtains, and hydro-thermal method can also be used to prepare.
In above-mentioned technical proposal, further comprise (4) 0.01~1 parts of sodium sulphate, the addition of sodium sulphate further suppress
The generation of NOx during decyanation, and there is synergistic effect between sodium sulphate and tungsten oxide.It has been surprisingly found that it is all sodium
The sodium chloride of salt is all that the potassium sulfates of alkali metal sulfates finds no this effect.The sodium sulphate is using anhydride or contains
The form of the crystallization water can be with, but dosage, in terms of anhydride, what is used in embodiment is anhydride.
The preparation method of catalyst any one of above-mentioned technical proposal, including solution and carrier by copper-containing compound
Mixing, dry, roasting.
When the catalyst when containing tungsten oxide, preferable preparation method is as follows：Including by the solution and oxygen of copper-containing compound
Change tungsten and carrier mixing, dry, roasting.
More preferably first tungsten oxide is mixed with the solution of copper-containing compound, it is dry, obtain catalyst precursor, then with catalysis
Agent carrier mixed-forming, dry, roasting obtains catalyst.Namely the preparation method includes the following steps：
1) solution of copper-containing compound is mixed with tungsten oxide, it is dry, obtain catalyst precursor；
2) by catalyst precursor and catalyst carrier mixed-forming, through drying, roasting, catalyst is made.
When the catalyst further contains (4) 0.01~1 parts of sodium sulphate, the preparation method of the catalyst is preferably to wrap
Include and mix the solution of copper-containing compound and sodium sulphate with tungsten oxide and carrier, dry, roasting.More preferably first by tungsten oxide with containing
The solution of copper compound and sodium sulphate mixes, dry, obtains catalyst precursor, then with catalyst carrier mixed-forming, it is dry,
Roasting obtains catalyst, namely the preparation method includes the following steps：
I) solution of copper-containing compound and sodium sulphate is mixed with tungsten oxide, it is dry, obtain catalyst precursor；
Ii) by catalyst precursor and catalyst carrier mixed-forming, through drying, roasting, catalyst is made.
It was found that using including above-mentioned steps 1) or the i) ratio in terms of NOx generations are reduced of catalyst made from which
The catalyst effect that directly copper compound solution is obtained with the mode that tungsten oxide and carrier mix is more preferable.
Dry temperature is not particularly limited in above-mentioned technical proposal, and such as, but not limited to dry temperature is 60~110
DEG C, the dry time is not particularly limited, such as, but not limited to 6~24 it is small when.
In above-mentioned technical proposal, the process conditions of roasting are not particularly limited, and the temperature such as, but not limited to roasted is 300
~800 DEG C, when the time of roasting is such as, but not limited to 2~8 small.
In above-mentioned technical proposal, to step 2) and ii) method of mixed-forming is not particularly limited, those skilled in the art
It can be reasonably selected in well known method, the shaping assistant such as, but not limited to added including binding agent is mixed
Pinch, extrude or catalyst is molded the methods of beating piece.
In above-mentioned technical proposal, the solvent used in the solution is not particularly limited, as long as can to required composition
Dissolving, in terms of economy and security standpoint, preferred water.For ease of year-on-year, the solvent in the specific embodiment of the invention is
Water.
In above-mentioned technical proposal, the copper-containing compound is preferably mantoquita.
In above-mentioned technical proposal, the mantoquita preferably is selected from least one in copper nitrate, copper chloride, copper sulphate and copper acetate
Kind.
The key problem in technology of the present invention is catalyst component, and the further selection of preparation method, to it in HCN-containing gases
On the basis of present disclosure, those skilled in the art can rationally be selected process conditions in catalysis oxidation decyanation
Select.
In above-mentioned technical proposal, the oxidant is preferably air or oxygen-enriched.
In above-mentioned technical proposal, the temperature of the reaction is preferably 280~500 DEG C.
In above-mentioned technical proposal, with HCN-containing gases and oxidant combined feed stereometer, air speed is 1000~30000h-1。
In above-mentioned technical proposal, the species of cyanogen in HCN-containing gases is not limited, as long as contain C ≡ N groups in molecule
The effect of removing is respectively provided with, 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..
Total amount containing cyanogen is not particularly limited in catalyst of the present invention, can reach year-on-year technology using catalyst of the present invention
Effect, for ease of year-on-year, the model gas of the HCN-containing gases used in the specific embodiment of the invention is by air, acrylonitrile and cyaniding
Hydrogen mixes, and wherein acrylonitrile content is 1925mg/m3, hydrogen cyanide content 240mg/m3。
It is 390 DEG C in reaction temperature, air speed 10000h-1, the model gas of HCN-containing gases is after catalyst treatment of the present invention, and third
Alkene nitrile is from 1,925mg/m3It is down to 0.4mg/m3；Hydrogen cyanide is from 240mg/m3It is down to 1.3mg/m3, NOx content is in tail gas
16.2mg/m3, achieve preferable technique effect.
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, TiO2:CuO is 85:15 prepare catalyst.
It will be equivalent to the Cu (NO containing 15 parts of CuO3)2With 85 parts of TiO2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts
Water mixes, extruded moulding after mediating 30 minutes, after drying at room temperature, 500 DEG C of roasting 4h, and the circle of obtained a diameter of a length of 1cm of 0.5cm
Cylindrical catalyst, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 2】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3For 85:15 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
By 15 parts of WO3With 85 parts of TiO2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water mixing, after mediating 30 minutes
Extruded moulding, after drying at room temperature, 500 DEG C of roasting 4h, are made the cylindrical catalyst of a diameter of a length of 1cm of 0.5cm, for ease of than
Compared with the composition of catalyst and preparation characteristic are listed in table 1.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 3】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO is 85:10:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 10 parts of WO3With the catalyst precursor and 85 parts of TiO of 5 parts of CuO2, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 4】
1st, catalyst preparation
In terms of weight proportion, Al2O3:WO3:CuO is 85:10:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 10 parts of WO3With the catalyst precursor and 85 parts of Al of 5 parts of CuO2O3, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 5】
1st, catalyst preparation
In terms of weight proportion, SiO2:WO3:CuO is 85:10:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 10 parts of WO3With the catalyst precursor and 85 parts of SiO of 5 parts of CuO2, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 6】
1st, catalyst preparation
In terms of weight proportion, ZrO2:WO3:CuO is 85:10:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO3)2100 parts of aqueous solution and 10 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 10 parts of WO3With the catalyst precursor and 85 parts of ZrO of 5 parts of CuO2, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 7】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO:Na2SO4For 85:9.95:5:0.05 prepares catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to contain 5 parts of CuO and 0.05 part of Na2SO4Cu (NO3)2100 parts and 9.95 parts of-sodium sulphate mixed aqueous solution
WO3Mixing, lower 80 DEG C of stirring is evaporated to no visual flow water, and when 80 DEG C of dryings 12 are small, catalyst precursor is made.
It will be equivalent to contain 9.95 parts of WO3, 5 parts of CuO and 0.05 part of Na2SO4Catalyst precursor and 85 parts of TiO2, 0.5 part
Carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, after drying at room temperature, 500 DEG C of roasting 4h,
The cylindrical catalyst of a diameter of a length of 1cm of 0.5cm is made, for ease of comparing, the composition of catalyst and preparation characteristic are listed in
Table 1.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Comparative example 1】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO:Na2SO4For 85:9.95:5:0.05 prepares catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO and 0.05 part of NaCl3)2100 parts and 9.95 parts of-sodium chloride mixed aqueous solution
WO3Mixing, lower 80 DEG C of stirring is evaporated to no visual flow water, and when 80 DEG C of dryings 12 are small, catalyst precursor is made.
It will be equivalent to contain 9.95 parts of WO3, 5 parts of CuO and 0.05 part of NaCl catalyst precursor and 85 parts of TiO2, 0.5 part of carboxylic
Methylcellulose, 2 parts of nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, after drying at room temperature, 500 DEG C of roasting 4h, and system
The cylindrical catalyst of a diameter of a length of 1cm of 0.5cm is obtained, for ease of comparing, the composition of catalyst and preparation characteristic are listed in table
1。
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Comparative example 2】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO:K2SO4For 85:9.95:5:0.05 prepares catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to contain 5 parts of CuO and 0.05 part of K2SO4Cu (NO3)2100 parts and 9.95 parts of-potassium sulfate mixed aqueous solution
WO3Mixing, lower 80 DEG C of stirring is evaporated to no visual flow water, and when 80 DEG C of dryings 12 are small, catalyst precursor is made.
It will be equivalent to contain 9.95 parts of WO3, 5 parts of CuO and 0.05 part of K2SO4Catalyst precursor and 85 parts of TiO2, 0.5 part
Carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, after drying at room temperature, 500 DEG C of roasting 4h,
The cylindrical catalyst of a diameter of a length of 1cm of 0.5cm is made, for ease of comparing, the composition of catalyst and preparation characteristic are listed in
Table 1.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Comparative example 3】
1st, catalyst preparation
In terms of weight proportion, TiO2:Na2SO4For 85:15 prepare catalyst.
By 15 parts of Na2SO4With 85 parts of TiO2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water mixing, mediate 30 points
Extruded moulding after clock, after drying at room temperature, 500 DEG C of roasting 4h, are made the cylindrical catalyst of a diameter of a length of 1cm of 0.5cm, for just
In comparing, the composition of catalyst and preparation characteristic are listed in table 1.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 8】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO is 75:20:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO3)2100 parts of aqueous solution and 20 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 20 parts of WO3With the catalyst precursor and 75 parts of TiO of 5 parts of CuO2, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 9】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO is 60:35:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 5 parts of CuO3)2100 parts of aqueous solution and 35 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 35 parts of WO3With the catalyst precursor and 60 parts of TiO of 5 parts of CuO2, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 10】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO is 60:30:10 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
It will be equivalent to the Cu (NO containing 10 parts of CuO3)2100 parts of aqueous solution and 30 parts of WO3Mixing, lower 80 DEG C of stirring are evaporated to nothing
Visual flow water, when 80 DEG C of dryings 12 are small, is made catalyst precursor.
It will be equivalent to contain 30 parts of WO3With the catalyst precursor and 60 parts of TiO of 10 parts of CuO2, 0.5 part of carboxymethyl cellulose, 2
Part nitric acid and 15 parts of water mix, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of
The cylindrical catalyst of a length of 1cm of 0.5cm, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 11】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO is 85:10:5 prepare catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
By 10 parts of WO3, 5 parts of CuO, 85 parts of TiO2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15 parts of water mixing, mediate 30
Extruded moulding after minute, after drying at room temperature, 500 DEG C of roasting 4h, are made the cylindrical catalyst of a diameter of a length of 1cm of 0.5cm, are
Easy to compare, the composition of catalyst and preparation characteristic are listed in table 1.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
【Embodiment 12】
1st, catalyst preparation
In terms of weight proportion, TiO2:WO3:CuO:Na2SO4For 85:9.95:5:0.05 prepares catalyst.
Hexagonal phase tungsten oxide nano (WO3) preparation：
2.13g ammonium tungstates, 8.32g ammonium sulfate and 2.10g oxalic acid are dissolved in 80mL water, are transferred to until completely dissolved
In 100mL autoclaves, 180 DEG C are warming up to, stirs 12h, after being cooled to room temperature, distills water washing 6 times, 100 DEG C with 100mL respectively
It is dried overnight, WO is made3。
By 9.95 parts of WO3, 5 parts of CuO, 0.05 part of Na2SO4, 85 parts of TiO2, 0.5 part of carboxymethyl cellulose, 2 parts of nitric acid and 15
Part water mixes, extruded moulding after mediating 30 minutes, and after drying at room temperature, 500 DEG C of roasting 4h, are made a diameter of a length of 1cm's of 0.5cm
Cylindrical catalyst, for ease of comparing, table 1 is listed in by the composition of catalyst and preparation characteristic.
2nd, evaluating catalyst
HCN-containing gases model gas (acrylonitrile 1925mg/m3, hydrogen cyanide 240mg/m3) by being filled with 800mL catalyst
Fixed bed reactors.Reaction temperature in reactor is 390 DEG C, reaction velocity 10000h-1.Reaction result is shown in Table 1.
Table 1
Note：I represents that the solution of copper-containing compound is first mixed with tungsten oxide in preparation process column；II represents copper-containing compound
Solution, tungsten oxide, carrier are mixed together；-- expression is not related to I and II.
Claims (10)
1. the removal methods of HCN-containing gases, in the presence of a catalyst, make HCN-containing gases and oxygenous oxidant in reactor
Cyanide in middle reaction removing exhaust gas, the catalyst, in parts by weight, including following components：
(1) 10~90 part of catalyst carrier；
(2) 0.1~20 parts of cupric oxide.
2. removal methods according to claim 1, it is characterized in that the catalyst carrier is selected from TiO2、ZrO2、SiO2With
Al2O3In one kind.
3. removal methods according to claim 1, it is characterized in that the catalyst is honeycomb type, trifolium-shaped, column
It is or spherical.
4. the removal methods described in claims 1 to 3, it is characterized in that the preparation method of the catalyst is included copper-containing compound
Solution mixed with carrier, dry, roasting.
5. removal methods according to claim 4, it is characterized in that the temperature of roasting is 300~800 DEG C.
6. removal methods according to claim 4, it is characterized in that when the time of roasting is 2~8 small.
7. removal methods according to claim 4, it is characterized in that the copper-containing compound is mantoquita.
8. removal methods according to claim 7, it is characterized in that the mantoquita be selected from copper nitrate, copper chloride, copper sulphate and
At least one of copper acetate.
9. removal methods according to claim 1, it is characterized in that the oxidant is preferably air or oxygen-enriched.
10. removal methods according to claim 1, it is characterized in that the temperature of the reaction is preferably 280~500 DEG C.
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