CN103785374B - A kind of C nano pipe demercuration catalyst and preparation method thereof - Google Patents
A kind of C nano pipe demercuration catalyst and preparation method thereof Download PDFInfo
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- CN103785374B CN103785374B CN201410057491.3A CN201410057491A CN103785374B CN 103785374 B CN103785374 B CN 103785374B CN 201410057491 A CN201410057491 A CN 201410057491A CN 103785374 B CN103785374 B CN 103785374B
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Abstract
The present invention discloses a kind of C nano pipe demercuration catalyst and preparation method thereof, and this catalyst comprises carrier and is attached to the active material in carrier, and described carrier is CNT, and described active material is the oxide of cerium and chromium; The oxide of described cerium generates after the soluble-salt roasting by cerium, and the oxide of chromium generates after the soluble-salt roasting by chromium.The preparation method of C nano pipe is as follows: with the soluble-salt of the soluble-salt of CNT, cerium and chromium for raw material, the mol ratio of Ce element and Cr element is 4 ~ 1:1, immersion treatment is carried out to CNT with red fuming nitric acid (RFNA), adds the soluble-salt of the soluble-salt of cerium and chromium dipping, dry, roasting obtains middle temperature demercuration catalyst.This catalyst has higher activity and selectivity between 300 ~ 400 DEG C, and therefore, be highly suitable for the SCR denitration device that low ash is arranged, these catalyst raw material wide material sources, preparation technology are simple, is a kind of well middle temperature catalyst.
Description
Technical field
The present invention relates to flue gas demercuration technical field, be specifically related to a kind of C nano pipe demercuration catalyst and preparation method thereof.
Background technology
Mercury is the unique liquid metal element of nature, and fusing point only has-38.89 DEG C.It as a kind of noxious material history for a long time, belong to the row of the strongest trace element of toxicity.Although the pollution of mercury to ecological environment is slowly, after entering air, water body and soil, can assembles in vivo, cause serious harm to human ecological environment.Up-to-date " the long atmosphere pollutants emission standards of thermoelectricity (GB13223-2011) " of Environment Protect in China cloth promulgated by the ministries or commissions of the Central Government, requires from 2015, controls mercury in power plant soot fume and compound emission amount at 0.03mg/nm
3.
For the emission control of combustion product gases mercury, demercuration method comparatively ripe at present has SCR catalytic oxidation and take active carbon as the absorption method of representative.Due to active carbon adsorption there is low capacity, Combination is poor, the feature of low thermodynamic stability, and the utilization rate of active carbon is low, consumption is large, direct use activated adoption method high cost.The SCR that the SCR that SCR demercuration technology can be divided into high ash to arrange according to position difference, low ash are arranged and the SCR that end is arranged.But due to the restriction of demercuration temperature, most factory faces adopt high ash to arrange.In China, because the shortage that clean coal technology uses, after coal combustion, fly ash content is very high.Directly cause catalysis to block passivation serious, catalyst is shorter than abroad service life, and power plant's demercuration cost significantly increases.
Summary of the invention
For the problems referred to above that prior art exists, an object of the present invention is the deficiency existed for present demercuration technical field, provide a kind of high selectivity, strong anti-Poisoning, the demercuration catalyst that reactivity worth is excellent, is applicable to the demercuration of various stationary source.
Another object is to provide a kind of method preparing above-mentioned demercuration catalyst.
For achieving the above object, the present invention adopts following technical scheme: a kind of C nano pipe demercuration catalyst, and comprise carrier and be attached to the active material in carrier, described carrier is CNT, and described active material is the oxide of cerium and chromium; The oxide of described cerium generates after the soluble-salt roasting by cerium, and the oxide of chromium generates after the soluble-salt roasting by chromium.Carbon nanotube forms the carrier shell of catalyst, the active nanoparticles kernel of the oxide composition catalyst of cerium and chromium.
As optimization, the mol ratio of the soluble-salt of described CNT, water, cerium and the soluble-salt of chromium is: 1:10 ~ 1000: 0.0001 ~ 0.4:0.0001 ~ 0.1.Catalyst active component is configured in rational scope, reaches excellent demercuration effect, save activator raw material simultaneously.
As optimization, CNT is single-walled nanotube or many walls nanotube, increases its surface area, and improve its catalytic activity, carbon nanotube diameter is between 8 ~ 10nm.
Prepare a method for above-mentioned C nano pipe demercuration catalyst, comprise the following steps:
1) with the soluble-salt of the soluble-salt of carbon nanotube, water, cerium and chromium for raw material, with mass fraction be first 60% ~ 90% red fuming nitric acid (RFNA) purification process is carried out to CNT, and stir 2 ~ 10 hours in the water bath with thermostatic control of 70 ~ 90 DEG C, then be 6 ~ 7 with deionized water rinsing to pH, finally dry at 60 ~ 150 DEG C;
2) infusion process carrying active substance is on the carbon nanotubes adopted, be specially: first the soluble-salt of the soluble-salt of cerium and chromium is configured to cerium solution and chromium solution respectively, then the CNT that step 1) obtains is joined in the mixed solution of cerium solution and chromium solution and stir dipping 2 ~ 20 hours, then dry at 60 ~ 150 DEG C, calcination 2 ~ 10 hours under last nitrogen protection, calcination temperature is 300 ~ 700 DEG C, obtain catalyst sample, wherein, the mol ratio of Ce elements and chromium element is 4 ~ 1:1, the mol ratio of Ce elements and chromium element sum and carbon element is 0.01 ~ 0.5:1.
As optimization, in described step 1) the soluble-salt of cerium be in cerous nitrate, ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate and cerous acetate one or more; The soluble-salt of described chromium be in chromic nitrate, chromium carbonate, manganese sulfate chromium one or more.Catalyst active component wide material sources are easy to buy and preparation, if when the soluble-salt of the soluble-salt of cerium and chromium adopts multiple soluble-salt mixed preparing, in various soluble-salt, Ce and Cr mol ratio calculates income value in the scope of above-mentioned requirements.
Relative to prior art, tool of the present invention has the following advantages:
1, demercuration catalyst provided by the invention is the catalyst of carbon based material cerium-carrying, chromium, this catalyst has higher activity and selectivity between 300 ~ 400 DEG C, therefore the SCR denitrification apparatus that low ash is arranged is highly suitable for, these catalyst raw material wide material sources, preparation technology are simple, are a kind of well middle temperature catalysts.
2, demercuration catalyst provided by the invention is the breakthrough in demercuration technical field, and proposing with carbon based material is first carrier loaded active material demercuration, and no longer place one's entire reliance upon traditional active carbon adsorption and titanium tungsten base SCR catalyst, has good application prospect.
3, due to special confinement effect and quantum effect, the growth of active nanoparticles suffers restraints, and its size diminishes, and contributes to generating more Donna rice grain defect and Lacking oxygen, and its catalytic activity strengthens, and the selective of reaction also effectively strengthens.Once the oxide of cerium and chromium enters confinement space in CNT, its catalytic activity and selectively all will effectively to strengthen.
4, excellent anti-poisoning capability.Compared with various traditional graininess demercuration catalyst, solid-state noxious material completely cuts off outside tube wall by the tube wall of the demercuration catalyst of C nano pipe provided by the invention, make it cannot contact the active nanoparticles being positioned at pipe interior, avoid the toxic action of poisonous substance to active nanoparticles.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
embodiment 1:
Catalyst raw material is CNT, water, cerous acetate, cerous nitrate and chromic nitrate.The advantages such as CNT obtains with chemical vapour deposition technique, and it is controlled that this method has preparation condition, easy batch production, the diameter of CNT is between 8 ~ 10nm.First soak CNT with the red fuming nitric acid (RFNA) of 68%, and stir 2 hours in the water bath with thermostatic control of 70 DEG C, be then 6 with deionized water rinsing to pH, finally dry at 60 DEG C.Get the CNT of 2 grams of red fuming nitric acid (RFNA) process; toward wherein adding 0.2 gram of cerous acetate, 0.2g cerous nitrate (the water-soluble solution with appropriate) and 0.2 gram of chromic nitrate (adding 5ml saturated oxalic acid solubilize); stir and flood 80 DEG C of oven dry after 2 hours, then namely 300 DEG C of calcinations obtain finished catalyst in 3 hours under nitrogen protection.
The catalyst of preparation is put into fixed bed quartz tube reactor and carries out activity and selectivity test.Flue gas condition is reaction condition: total gas flow rate is 1L/min, and mercury concentration is 50ug/m
3, C
o2=4%, C
cO2=12%, C
hCl=5ppm, C
sO2=400ppm, C
nO=150ppm, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 300 ~ 400 DEG C, reaction temperature interval, demercuration rate is stabilized in more than 85%.
embodiment 2:
Catalyst raw material is CNT, water, cerous nitrate, cerous sulfate and chromium carbonate.CNT obtains with chemical vapour deposition technique, first soaks CNT with the red fuming nitric acid (RFNA) of 80%, and stirs 4 hours in the water bath with thermostatic control of 80 DEG C, is then 6.5 with deionized water rinsing to pH, finally dries at 80 DEG C.Get the CNT of 2 grams of red fuming nitric acid (RFNA) process; toward wherein adding 1 gram of cerous nitrate, 0.5g cerous sulfate (the water-soluble solution with appropriate) and 0.1 gram of chromium carbonate (adding 5ml saturated oxalic acid solubilize); stir and flood 60 DEG C of oven dry after 5 hours, then namely 400 DEG C of calcinations obtain finished catalyst in 3 hours under nitrogen protection.
The catalyst of preparation is put into fixed bed quartz tube reactor and carries out activity and selectivity test.Flue gas condition is reaction condition: total gas flow rate is 1L/min, and mercury concentration is 50ug/m
3, C
o2=4%, C
cO2=12%, C
hCl=5ppm, C
sO2=400ppm, C
nO=150ppm, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 300 ~ 400 DEG C, reaction temperature interval, demercuration rate is stabilized in more than 85%.
embodiment 3:
Catalyst raw material is CNT, water, cerous nitrate and manganese sulfate chromium.CNT obtains with chemical vapour deposition technique, first soaks CNT with the red fuming nitric acid (RFNA) of 85%, and stirs 8 hours in the water bath with thermostatic control of 80 DEG C, is then 7 with deionized water rinsing to pH, finally dries at 100 DEG C.Get the CNT of 2 grams of red fuming nitric acid (RFNA) process; toward wherein adding 0.2 gram of cerous nitrate (the water-soluble solution with appropriate) and 0.1 gram of manganese sulfate chromium (adding 5ml saturated oxalic acid solubilize); stir and flood 100 DEG C of oven dry after 10 hours, then namely 550 DEG C of calcinations obtain finished catalyst in 3 hours under nitrogen protection.
The catalyst of preparation is put into fixed bed quartz tube reactor and carries out activity and selectivity test.Flue gas condition is reaction condition: total gas flow rate is 1L/min, and mercury concentration is 50ug/m
3, C
o2=4%, C
cO2=12%, C
hCl=5ppm, C
sO2=400ppm, C
nO=150ppm, NH
3/ NO=1:1, N2 are as balanced gas, and air speed is 60000h
-1.In 300 ~ 400 DEG C, reaction temperature interval, demercuration rate is stabilized in more than 80%.
embodiment 4:
Catalyst raw material is CNT, water, cerous sulfate, ammonium ceric nitrate and chromic nitrate.CNT obtains with chemical vapour deposition technique, first soaks CNT with the red fuming nitric acid (RFNA) of 90%, and stirs 10 hours in the water bath with thermostatic control of 90 DEG C, is then 7 with deionized water rinsing to pH, finally dries at 150 DEG C.Get the CNT of 2 grams of red fuming nitric acid (RFNA) process; toward wherein adding 2 grams of ammonium ceric nitrates, 1 gram of cerous sulfate (the water-soluble solution with appropriate) and 0.2 gram of chromic nitrate (adding 5ml saturated oxalic acid solubilize); stir and flood 120 DEG C of oven dry after 20 hours, then namely 700 DEG C of calcinations obtain finished catalyst in 3 hours under nitrogen protection.
The catalyst of preparation is put into fixed bed quartz tube reactor and carries out activity and selectivity test.Flue gas condition is reaction condition: total gas flow rate is 1L/min, and mercury concentration is 50ug/m
3, C
o2=4%, C
cO2=12%, C
hCl=5ppm, C
sO2=400ppm, C
nO=150ppm, NH
3/ NO=1:1, N
2as balanced gas, air speed is 60000h
-1.In 300 ~ 400 DEG C, reaction temperature interval, demercuration rate is stabilized in more than 85%.
Tested can be found out by above-described embodiment and activity and selectivity, CNT demercuration is feasible.Its demercuration rate can reach about 80%.Meanwhile, these catalyst raw material wide material sources, preparation technology are simple, are a kind of well middle temperature catalysts.There is potential commercial researching value and Practical significance.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (4)
1. a C nano pipe demercuration catalyst, is characterized in that: comprise carrier and be attached to the active material in carrier, described carrier is CNT, and described active material is the oxide of cerium and chromium; The oxide of described cerium generates after the soluble-salt roasting by cerium, and the oxide of chromium generates after the soluble-salt roasting by chromium;
The mol ratio of Ce elements and chromium element is 4 ~ 1:1, and the mol ratio of Ce elements and chromium element sum and carbon is 0.01 ~ 0.5:1.
2. C nano pipe demercuration catalyst as claimed in claim 1, is characterized in that: described CNT is single-walled nanotube or many walls nanotube.
3. prepare a method for C nano pipe demercuration catalyst according to claim 1, it is characterized in that, comprise the following steps:
1) with the soluble-salt of the soluble-salt of CNT, water, cerium and chromium for raw material, with mass fraction be first 60% ~ 90% red fuming nitric acid (RFNA) purification process is carried out to CNT, and stir 2 ~ 10 hours in the water bath with thermostatic control of 70 ~ 90 DEG C, then be 6 ~ 7 with deionized water rinsing to pH, finally dry at 60 ~ 150 DEG C;
2) infusion process carrying active substance is on the carbon nanotubes adopted, be specially: first the soluble-salt of the soluble-salt of cerium and chromium is configured to cerium solution and chromium solution respectively, then the CNT that step 1) obtains is joined in the mixed solution of cerium solution and chromium solution and stir dipping 2 ~ 20 hours, then dry at 60 ~ 150 DEG C, last calcination under nitrogen protection 2 ~ 10 hours, calcination temperature is 300 ~ 700 DEG C, obtain catalyst sample, wherein, the mol ratio of Ce elements and chromium element is 4 ~ 1:1, the mol ratio of Ce elements and chromium element sum and carbon is 0.01 ~ 0.5:1.
4. prepare as claimed in claim 3 the method for C nano pipe demercuration catalyst, it is characterized in that: in described step 1) the soluble-salt of cerium be in cerous nitrate, ammonium ceric nitrate, cerous sulfate, Cericammoniumsulfate and cerous acetate one or more; The soluble-salt of described chromium be in chromic nitrate, chromium carbonate, manganese sulfate chromium one or more.
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