CN105251543B - A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning - Google Patents
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 238000011069 regeneration method Methods 0.000 title claims abstract description 24
- 208000008316 Arsenic Poisoning Diseases 0.000 title claims abstract description 19
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 40
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 230000002779 inactivation Effects 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 26
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 25
- 229960002594 arsenic trioxide Drugs 0.000 claims description 25
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 claims description 24
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229950008475 oxophenarsine Drugs 0.000 claims description 24
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 2
- DLCOPLYGCSRNAY-UHFFFAOYSA-N molybdenum titanium vanadium Chemical compound [Ti][Mo][V] DLCOPLYGCSRNAY-UHFFFAOYSA-N 0.000 claims description 2
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 20
- 230000008929 regeneration Effects 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 208000005374 Poisoning Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- -1 arsenic oxide arsenoxides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Decaying catalyst duct is first utilized iron wire and giant deashing by a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, removes surface and the remaining silica in duct, calcium sulfate and organic residue impurity, for use after air drying；Then dry decaying catalyst is placed in tube furnace, in H2/ He atmosphere roasts, and the catalyst of removing arsenic is obtained after Temperature fall；Finally the catalyst of removing arsenic takes out, after 110 DEG C of dry 2h, it is placed in air atmosphere and roasts, obtain regenerated catalyst, the present invention can be widely applied to a variety of denitrating catalysts that arsenic causes inactivation, and is regenerated by simple hydrogen reducing and extend catalyst service life and without solvent and active supplement process.
Description
Technical field
The present invention relates to the denitrating catalyst technical field of regeneration in atmospheric environment protection, and in particular to a kind of arsenic poisoning is de-
Sell the hydrogen reducing regeneration method of catalyst.
Background technology
Studies have shown that nitrogen oxides (NOx) is the important as precursors for causing nitric acid type acid rain, photochemical fog and haze weather
Object discharges the burning essentially from coal, and thermal power plant's NOx yields are the half of national total amount, therefore, thermal power plant NOx
Emission control is the key that China's NOx emission control.Selective catalytic reduction (SCR) is used as most efficient denitration technology, always
It is the first choice of domestic and international coal fired power plant vent gas treatment.However denitrating catalyst General Life is 24000 hours；Furthermore it is contemplated that
In the end of the year 2015, denitrating catalyst usage amount is up to ten thousand m of 60-80 in coal-burning power plant3.If a large amount of waste catalysts directly filled out
If burying, significant wastage that is not only of high cost but also causing resource, therefore regenerate as best dead catalyst processing mode.
Noble metal arsenic As not only has higher physiological-toxicity, and very big for denitrating catalyst activity influence.Research
Show that the mass fraction of arsenic in coal is more than 30ppm, SCR catalyst chemical lifetime will reduce by 50% or so.Although arsenic content in coal
With coal difference, there are deviations, and in general, the poisoned catalyst arsenic oxide arsenoxide content after work in 24000 hours is arrived 0
Between 3wt%.If directly filled without processing, there is very big hidden danger to underground water and soil safety.Traditional sulfuric acid is clear
Wash, cannot not only remove and be stored in catalyst pores and the arsenic species on surface, and can cause loss of active component, equipment corrosion and
Intensity declines.Therefore the new and effective regeneration method suitable for As poisoning denitrating catalysts is developed, realizes that resource circulation utilization is ten
Divide necessary.
Invention content
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of out of stock catalyst of arsenic poisoning
Hydrogen reducing regeneration method can be widely applied to arsenic and cause a variety of (vanadium base, cerium base etc.) denitrating catalysts of inactivation, and passes through letter
Single hydrogen reducing regeneration extends catalyst service life and without solvent and active supplement process.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, includes the following steps：
Step 1：Decaying catalyst duct is utilized into iron wire and giant deashing, removes surface and the remaining oxygen in duct
SiClx, calcium sulfate and organic residue impurity, it is for use after air drying；
Step 2：The obtained dry decaying catalyst of step 1 is placed in tube furnace, in H2/ He atmosphere roasts, specifically
Condition：Hydrogen volume ratio accounts for H2Between the 0-100% of/He atmosphere, H2Between/He gas flows 0-100ml/min, heating rate
For 1-30 DEG C/min, 400-650 DEG C is risen to from room temperature, and be held in the temperature calcination, roasting time is natural between 0-10h
The catalyst of removing arsenic is obtained after cooling；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere
Middle roasting, roasting condition：Between gas flow 0-50ml/min, heating rate is 1-50 DEG C/min, calcination temperature 300-600
DEG C, roasting time obtains regenerated catalyst between 0-10h.
Compared with prior art, the invention has the advantages that：
1. the present invention is not necessarily to any regenerated liquid, operation is easy, and As removal rates are high, is suitable for multiclass denitrating catalyst, especially
It is re-used after being suitable for the denitrating catalyst regeneration of high As poisonings.
2. the present invention can retain most vanadium oxide, tungsten oxide isoreactivity component while a large amount of arsenic removes,
And it can be omitted the active implantation step in the later stage of conventional regeneration technology.
It, being capable of efficient removal nitrogen oxides (conversion rate of NOx highest under the premise of inactive implantation step>90%) and it is real
Existing efficient oxidation arsenic removes (As2O3Removal rate highest>90%).
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, includes the following steps：
Step 1：Vanadium tungsten titanium or vanadium molybdenum titanium catalyst are prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3
After solution impregnation drying, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, then by the catalyst of arsenic poisoning in 450 degree of roastings
After burning 3h fixation arsenic oxide arsenoxides, it is ground up, sieved, obtains 40-60 mesh decaying catalysts；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio
Account for H210%, H of/He atmosphere2/ He gas flows are 80mL/min, and heating rate is 20 DEG C/min, and 500 DEG C are risen to from room temperature,
And in 500 DEG C of roastings, 2h is kept, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere
Middle roasting, roasting condition：Gas flow 20ml/min, heating rate are 5 DEG C/min, and calcination temperature is 500 DEG C, and roasting time is
2 hours, obtain regenerated catalyst.
Embodiment 2
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, includes the following steps：
Step 1：Cerium tungsten titanium catalyst is prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution impregnates
After drying, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, after 450 degree of roasting 3h fix arsenic oxide arsenoxide, is ground up, sieved, obtains 40-60
Mesh decaying catalyst；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio
Account for H25%, H of/He atmosphere2/ He gas flows are under the atmosphere of 50mL/min, and heating rate is 10 DEG C/min, is risen to from room temperature
600 DEG C, and in 600 DEG C of roastings, keep 20min, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere
Middle roasting, roasting condition：Gas flow 50ml/min, heating rate are 10 DEG C/min, and calcination temperature is 600 DEG C, roasting time
It is 4 hours, obtains regenerated catalyst.
Embodiment 3
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, includes the following steps：
Step 1：Cerium tungsten titanium catalyst is prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution impregnates
After drying, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, after 450 degree of roasting 3h fix arsenic oxide arsenoxide, is ground up, sieved, obtains 40-60
Mesh decaying catalyst；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio
Account for H240%, H of/He atmosphere2/ He gas flows are 90mL/min, and heating rate is 30 DEG C/min, and 550 DEG C are risen to from room temperature,
And in 550 DEG C of roastings, 5h is kept, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere
Middle roasting, roasting condition：Gas flow 10ml/min, heating rate are 40 DEG C/min, and calcination temperature is 500 DEG C, roasting time
It is 2 hours, obtains regenerated catalyst.
Embodiment 4
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, includes the following steps：
Step 1：Vanadium tungsten titanium catalyst is prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution impregnates
After drying, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, after 450 degree of roasting 3h fix arsenic oxide arsenoxide, is ground up, sieved, obtains 40-60
Mesh decaying catalyst；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio
Account for H280%, H of/He atmosphere2/ He gas flows are 60mL/min, and heating rate is 10 DEG C/min, and 500 DEG C are risen to from room temperature,
And in 500 DEG C of roastings, 20min is kept, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere
Middle roasting, roasting condition：Gas flow 50ml/min, heating rate are 10 DEG C/min, and calcination temperature is 500 DEG C, roasting time
It is 8 hours, obtains regenerated catalyst.
Embodiment 5
A kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, includes the following steps：
Step 1：It causes inactivation enterprise's vanadium tungsten titanium catalyst duct to utilize iron wire and giant deashing arsenic, removes surface
With the remaining silica in duct, calcium sulfate and organic residue impurity, it is 3 × 3 to be cut into hole count, and length is the small catalyst of 100mm
Dried for standby；
Step 2：The obtained decaying catalyst of 10g step 1 is placed in tube furnace, in H2/ He atmosphere roasts, and roasts item
Part：Hydrogen volume ratio accounts for H21%, H of/He atmosphere2/ He gas flows are 10mL/min, and heating rate is 5 DEG C/min, from room temperature
600 DEG C are risen to, and in 600 DEG C of roastings, keeps 4h, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere
Middle roasting, roasting condition：Gas flow 30ml/min, heating rate are 5 DEG C/min, and calcination temperature is 500 DEG C, and roasting time is
3 hours, obtain regenerated catalyst.
The efficiency recovery rate contrast test of embodiment 1-5 regenerated catalysts：
It is compared using 350 DEG C of efficiency recovery rates of regenerated catalyst of embodiment 1-5, and is removed using XRF tests As
Rate, catalyst denitration efficiency, activation recovering rate and As removal rates are calculated as follows：
Denitration efficiency μ=([NOXin]-[NOXout])/[NOXin] × 100%
Activation recovering rate y=(μregenerated-μpoisoned)/μregenerated
As removal rate x=([As2O3poisoned]-[As2O3regenerated])/[As2O3poisoned] × 100%
Wherein：[NOXin] be Reactor inlet NOx concentration (ppm), [NOXout] be NOx in gas after processing concentration
(ppm).Test condition is：350 DEG C of temperature, normal pressure, reaction velocity 120000h-1, catalyst takes the 0.1g, flue gas concentration to be
500ppm NH3, 500ppm NO, 3%O2；[As2O3poisoned] be poisoned catalyst arsenic percentage composition (with As2O3),
[As2O3regenerated] be regenerated catalyst arsenic percentage composition (with As2O3).Table one is the experimental result of above-described embodiment.
Table one
| Embodiment | Denitration efficiency (%) | As removal rates (%) | Activation recovering rate (%) |
| 1 | 83 | 84.4 | 82% |
| 2 | 93 | 92.9 | 69.8% |
| 3 | 60 | 72.6 | 43.9 |
| 4 | 47 | 33.3 | 34.5 |
| 5 | 50 | 74.2 | 77.9 |
Table one the result shows that, 600 DEG C, 5%H2High temperature reduction can effectively clear vanadium base and ceria-based denitration catalyst under the conditions of/He
Arsenic, and effectively restore catalytic activity；And 500 DEG C and 550 DEG C of regeneration temperatures be although part arsenic can be removed, can only recovered part live
Property；For the waste and old poisoned catalyst of enterprise, hydrogen high temperature regeneration also obtains good result.
Claims (6)
1. a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning, which is characterized in that include the following steps：
Step 1：Decaying catalyst duct is utilized into iron wire and giant deashing, remove surface and the remaining silica in duct,
Calcium sulfate and organic residue impurity, it is for use after air drying；
Step 2：The obtained dry decaying catalyst of step 1 is placed in tube furnace, in H2/ He atmosphere roasts, actual conditions：
Hydrogen volume ratio accounts for H2Between the 1-100% of/He atmosphere, H2Between/He gas flows 10-100ml/min, heating rate 1-
30 DEG C/min, 400-650 DEG C is risen to from room temperature, and be held in the temperature calcination, roasting time is natural between 20min-10h
The catalyst of removing arsenic is obtained after cooling；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere and roasts
It burns, roasting condition：Between gas flow 0-50ml/min, heating rate is 1-50 DEG C/min, and calcination temperature is 300-600 DEG C,
Roasting time obtains regenerated catalyst between 2-8h.
2. a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning according to claim 1, which is characterized in that packet
Include following steps：
Step 1：Vanadium tungsten titanium or vanadium molybdenum titanium catalyst are prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution
After impregnation drying, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, and the catalyst of arsenic poisoning is then roasted 3h in 450 DEG C
After fixed arsenic oxide arsenoxide, it is ground up, sieved, obtains 40-60 mesh decaying catalysts；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio accounts for H2/
10%, H of He atmosphere2/ He gas flows are 80mL/min, and heating rate is 20 DEG C/min, and 500 DEG C are risen to from room temperature, and in
500 DEG C of roastings keep 2h, the catalyst of removing arsenic are obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere and roasts
It burns, roasting condition：Gas flow 20ml/min, heating rate are 5 DEG C/min, and calcination temperature is 500 DEG C, and roasting time is 2 small
When, obtain regenerated catalyst.
3. a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning according to claim 1, which is characterized in that packet
Include following steps：
Step 1：Cerium tungsten titanium catalyst is prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution impregnation drying
Afterwards, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, after 450 DEG C of roasting 3h fix arsenic oxide arsenoxide, is ground up, sieved, obtains the mistake of 40-60 mesh
Catalyst living；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio accounts for H2/
5%, H of He atmosphere2/ He gas flows are under the atmosphere of 50mL/min, and heating rate is 10 DEG C/min, and 600 are risen to from room temperature
DEG C, and in 600 DEG C of roastings, keep 20min, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere and roasts
It burns, roasting condition：Gas flow 50ml/min, heating rate are 10 DEG C/min, and calcination temperature is 600 DEG C, and roasting time is 4 small
When, obtain regenerated catalyst.
4. a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning according to claim 1, which is characterized in that packet
Include following steps：
Step 1：Cerium tungsten titanium catalyst is prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution impregnation drying
Afterwards, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, after 450 DEG C of roasting 3h fix arsenic oxide arsenoxide, is ground up, sieved, obtains the mistake of 40-60 mesh
Catalyst living；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio accounts for H2/
40%, H of He atmosphere2/ He gas flows are 90mL/min, and heating rate is 30 DEG C/min, and 550 DEG C are risen to from room temperature, and in
550 DEG C of roastings keep 5h, the catalyst of removing arsenic are obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere and roasts
It burns, roasting condition：Gas flow 10ml/min, heating rate are 40 DEG C/min, and calcination temperature is 500 DEG C, and roasting time is 2 small
When, obtain regenerated catalyst.
5. a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning according to claim 1, which is characterized in that packet
Include following steps：
Step 1：Vanadium tungsten titanium catalyst is prepared by the precipitation method first, then places it in arsenic oxide arsenoxide As2O3Solution impregnation drying
Afterwards, arsenic oxide arsenoxide As is obtained2O3Mass concentration is 3%, after 450 DEG C of roasting 3h fix arsenic oxide arsenoxide, is ground up, sieved, obtains the mistake of 40-60 mesh
Catalyst living；
Step 2：The decaying catalyst of 1g is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen volume ratio accounts for H2/
80%, H of He atmosphere2/ He gas flows are 60mL/min, and heating rate is 10 DEG C/min, and 500 DEG C are risen to from room temperature, and in
500 DEG C of roastings keep 20min, the catalyst of removing arsenic are obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere and roasts
It burns, roasting condition：Gas flow 50ml/min, heating rate are 10 DEG C/min, and calcination temperature is 500 DEG C, and roasting time is 8 small
When, obtain regenerated catalyst.
6. a kind of hydrogen reducing regeneration method of the out of stock catalyst of arsenic poisoning according to claim 1, which is characterized in that packet
Include following steps：
Step 1：It causes inactivation enterprise's vanadium tungsten titanium catalyst duct to utilize iron wire and giant deashing arsenic, removes surface and hole
The remaining silica in road, calcium sulfate and organic residue impurity, it is 3 × 3 to be cut into hole count, and the small catalyst that length is 100mm is dried
For use；
Step 2：The obtained decaying catalyst of 10g step 1 is placed in tube furnace, in H2/ He atmosphere roasts, roasting condition：Hydrogen
Air volume ratio accounts for H21%, H of/He atmosphere2/ He gas flows are 10mL/min, and heating rate is 5 DEG C/min, is risen to from room temperature
600 DEG C, and in 600 DEG C of roastings, keep 4h, the catalyst of removing arsenic is obtained after Temperature fall；
Step 3：The catalyst for the removing arsenic that step 2 obtains is taken out, after 110 DEG C of dry 2h, is placed in air atmosphere and roasts
It burns, roasting condition：Gas flow 30ml/min, heating rate are 5 DEG C/min, and calcination temperature is 500 DEG C, and roasting time is 3 small
When, obtain regenerated catalyst.
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| CN104857998A (en) * | 2015-06-02 | 2015-08-26 | 清华大学 | Efficient regenerating method for As-poisoned denitration catalyst |
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