CN109647144A - Liquid phase catalyst, preparation and application - Google Patents
Liquid phase catalyst, preparation and application Download PDFInfo
- Publication number
- CN109647144A CN109647144A CN201811595315.XA CN201811595315A CN109647144A CN 109647144 A CN109647144 A CN 109647144A CN 201811595315 A CN201811595315 A CN 201811595315A CN 109647144 A CN109647144 A CN 109647144A
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- China
- Prior art keywords
- liquid
- phase catalyst
- naclo
- catalyst
- denitration
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000007791 liquid phase Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000003002 pH adjusting agent Substances 0.000 claims description 17
- 239000012190 activator Substances 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000000520 microinjection Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000008569 process Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01D53/8625—Nitrogen oxides
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/202—Alkali metals
- B01D2255/2027—Sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The liquid phase catalyst comprises 15-30 wt% of activating agent, 1-6 wt% of pH regulator and the balance of water, and can be used for flue gas denitration reaction. The denitration liquid-phase catalyst provided by the invention captures NOx in a denitration reaction section and breaks the molecular chain of the NOx, and then reacts with a denitration liquid-phase reducing agent in a denitration high-efficiency reduction absorption tower to be reduced into N2And H2And O, the denitration efficiency is extremely high.
Description
Technical field
This disclosure relates to which a kind of low-temperature liquid phase catalytic reduction denitration field more particularly to a kind of reduction denitration of low temperature liquid phase are urged
Agent.
Background technique
Emerging biomass fermentation electric boiler, garbage power generation boiler and industrial enterprise, which provides for oneself in miniature boiler flue gas, contains SO2、
The pollutants such as NOx, it has also become new pollution sources.There are high risks to human body, environment and the ecosystem.With the day of environmental requirement
It is beneficial stringent, the problem of discharged nitrous oxides more and more attention has been paid to.Therefore, to biomass fermentation electric boiler, garbage power generation boiler and
Industrial enterprise provides miniature boiler SO for oneself2And the strict control of NOx discharge, it can effectively reduce the pollution level to atmosphere.
Currently, ultralow temperature liquid phase catalytic reduction method of denitration is that denitration efficiency is higher, the relatively broad one kind of business application
Method, in the method, the component and preparation process of catalyst are the core technologies of this method.In general, being related in this method
And catalyst include noble metal catalyst and non-precious metal catalyst.Noble metal catalyst reactivity is high, conversion temperature
It is lower but expensive, and non-precious metal catalyst is in contrast, cheap but reactivity is not often high.Therefore to the greatest extent may be used
It is technical problem underlying at this stage that the conversion ratio of NOx, which can be improved, and reduce catalyst cost.
NOx is captured in denitration reaction section and is broken its strand by denitration liquid-phase catalyst provided by the invention, so
It reacts with denitration liquid phase reducing agent in the efficient Reducing and absorption tower of denitration afterwards and is reduced into N2And H2O。
Reaction principle is as follows:
The subtractive process of NOx is point two completions in flue gas:
The first step, gas-liquid mass transfer and hydro-combination process, i.e., captured when NOx molecule and denitrfying agent contact in flue gas and by its
Strand is broken:
NOx+ denitration liquid-phase catalyst → N+·O+ (1)
Step 2: reduction
N+·O++ denitration liquid phase reducing agent=H20+N2↑ (2)
Summary of the invention
The present invention In view of the above shortcomings of the prior art, provides a kind of ultralow temperature liquid phase catalytic reduction denitrating catalyst
And application.
A kind of liquid-phase catalyst comprising activator, pH adjusting agent and water, the weight content of each component are activator
15%-30%, pH adjusting agent 1-6%, remaining be water.
In one embodiment, the activator is NaClO, NaClO2And H2O2One of or it is a variety of.
In one embodiment, the pH adjusting agent is one of dilute sulfuric acid or dilute hydrochloric acid or a variety of.
In one embodiment, the activator is NaClO, NaClO2And H2O2, pH adjusting agent is dilute sulfuric acid;Each component
Weight content is NaClO 17%, NaClO28.5%, H2O22.5%, H2SO42%.
A method of preparing the liquid-phase catalyst, comprising: mix the activator;The pH is adjusted
Agent is added in the intermixture using micro-injection pump;The aqueous solution is added.
In one embodiment, the addition rate of the pH adjusting agent is 10-20ml/h.
In one embodiment, the addition rate of the pH adjusting agent is 10ml/h.
Catalyst is placed in liquid-phase catalyst storage tank by a kind of application of liquid-phase catalyst, is measured and is pressurizeed by liquid-phase catalyst
The liquid-phase catalyst in liquid-phase catalyst storage tank is delivered to liquid-phase catalyst injection grid by pump, and flue gas enters liquid-phase catalysis
Agent injection grid is reacted with the liquid-phase catalyst, and reaction temperature is 65 DEG C -85 DEG C.
The utility model has the advantages that
Compared with traditional catalyst, the catalyst denitration activity that the method for the present invention prepares is strong, reaction rate is fast, desulfurization
Denitration efficiency is high, can make emission limit < 50mg/m of NOx3, it is far below national standard;Also, denitration temperature is low, can be low
The removing of lower completion oxynitrides in 90 DEG C the case where, is not limited, and denitration efficiency can achieve 90% by flue-gas temperature
More than.
Specific embodiment
Embodiment 1
Present invention liquid-phase catalyst used in the subtractive process of NOx in flue gas includes NaClO, dilute sulfuric acid and water,
Wherein NaClO is activator, and dilute sulfuric acid is pH adjusting agent, and the weight content of the above components is NaClO 29%, dilute sulfuric acid
1%, remaining is water.
The catalyst the preparation method comprises the following steps: by the dilute sulfuric acid of above-mentioned metering using micro-injection pump according to 20ml/h rate
It is added in the NaClO of above-mentioned metering, the water of above-mentioned metering is added in dilute sulfuric acid after injecting.The catalyst prepared using this method
Component is uniform, can effectively capture NOx, and its strand is interrupted, catalytic effect is good.
The process of liquid phase denitration reaction is carried out using the catalyst are as follows: 1 → N of NOx+ denitration liquid-phase catalyst+·O+;N+·O
+ denitration liquid phase reducing agent=H20+N2↑, reaction temperature is 77 DEG C, conversion rate of NOx 95%.
Specific reaction process is as follows:
Containing SO2And the industrial smoke of NOx enters liquid-phase catalyst by flue and sprays grid, sprays lattice in liquid-phase catalyst
It force (forcing) pump is measured by liquid-phase catalyst in grid completes denitration catalyst from the liquid-phase catalyst that the conveying of liquid-phase catalyst storage tank comes and react.
Flue gas after completing denitration catalyst reaction enters efficient Reducing and absorption desulfurizing tower, in efficient Reducing and absorption desulfurizing tower and through liquid phase
Reductant metering pump follows in reduction and desulfurization circulating pump with denitration from the liquid-phase reduction agent storage tank that the conveying of liquid-phase reduction agent storage tank comes
Desulphurization and denitration reaction is completed after the mixing of ring liquid, the flue gas after completing desulphurization and denitration passes through direct exhaust chimney qualified discharge.
Embodiment 2
Present invention liquid-phase catalyst used in the subtractive process of NOx in flue gas includes NaClO, NaClO2, dilute hydrochloric acid
And water, wherein NaClO and NaClO2For activator, dilute hydrochloric acid is pH adjusting agent, and the weight content of the above components is
NaClO 24%, NaClO 6%, dilute hydrochloric acid 6%, remaining is water.
The catalyst the preparation method comprises the following steps: by NaClO, NaClO of above-mentioned metering2Mixing, by the dilute hydrochloric acid of above-mentioned metering
Above-mentioned NaClO and NaClO is added according to the rate of 15ml/h using micro-injection pump2In, dilute hydrochloric acid is added after injecting
State the water of metering.The catalytic component prepared using this method is uniform, can effectively capture NOx, and its strand is interrupted, urge
It is good to change effect.
The process of liquid phase denitration reaction is carried out using the catalyst are as follows: 2 → N of NOx+ denitration liquid-phase catalyst+·O+;N+·
O+Denitration liquid phase reducing agent=H20+N2↑, reaction temperature is 73 DEG C, conversion rate of NOx 96%.
Specific reaction process is same as Example 1.
Embodiment 3
Present invention liquid-phase catalyst used in the subtractive process of NOx in flue gas includes NaClO2, dilute sulfuric acid and water,
Wherein NaClO2For activator, dilute sulfuric acid is pH adjusting agent, and the weight content of the above components is NaClO 15%, dilute sulfuric acid
5%, remaining is water.
The catalyst the preparation method comprises the following steps: by the dilute sulfuric acid of above-mentioned metering using micro-injection pump according to 20ml/h rate
The NaClO of above-mentioned metering is added2In, the water of above-mentioned metering is added in dilute sulfuric acid after injecting.The catalysis prepared using this method
Agent component is uniform, can effectively capture NOx, and its strand is interrupted, catalytic effect is good.
The process of liquid phase denitration reaction is carried out using the catalyst are as follows: 3 → N of NOx+ denitration liquid-phase catalyst+·O+;N+·
O+Denitration liquid phase reducing agent=H20+N2↑, reaction temperature is 85 DEG C, conversion rate of NOx 92%.
Specific reaction process is same as Example 1.
Embodiment 4
Present invention liquid-phase catalyst used in the subtractive process of NOx in flue gas includes NaClO, NaClO2, dilute sulfuric acid,
Hydrogen peroxide and water, wherein NaClO, NaClO2And hydrogen peroxide is activator, dilute sulfuric acid is pH adjusting agent, the above components
Weight content is NaClO 17%, NaClO28.5%, H2O22.5%, H2SO42%, remaining is water.
The catalyst the preparation method comprises the following steps: NaClO, NaClO2And hydrogen peroxide according to aforementioned proportion, i.e. active component is excellent
It is first mixed at normal temperature, forms homogeneous solution;Above-mentioned dilute sulfuric acid is added using micro-injection pump according to the rate of 10ml/h
Enter, the water of above-mentioned metering is added in dilute sulfuric acid after injecting.The catalytic component prepared using this method is uniform, can effectively catch
NOx is caught, and its strand is interrupted, catalytic effect is good.
The process of liquid phase denitration reaction is carried out using the catalyst are as follows: 4 → NO+ of NOx+ denitration liquid-phase catalyst;N+·O+
+ denitration liquid phase reducing agent=H20+N2↑, reaction temperature is 65 DEG C, conversion rate of NOx 98%.
Specific reaction process is same as Example 1.
Comparative example:
Catalyst in the prior art: carrier active carbon 80~99.9%, active component yttria 0.1~10%,
Co-catalyst 0~10%.The liquid-phase catalysis denitration reaction of the same terms is used with previous embodiment, reaction temperature is 400 DEG C,
Conversion rate of NOx is 90%..
Compared with the catalyst of the prior art, reaction temperature is lower.And transfer efficiency is also higher.
Claims (8)
1. a kind of liquid-phase catalyst, which is characterized in that including activator, pH adjusting agent and water, the weight content of each component is
Activator 15%-30%, pH adjusting agent 1-6%, remaining be water.
2. liquid-phase catalyst according to claim 1, which is characterized in that the activator is NaClO, NaClO2And H2O2
One of or it is a variety of.
3. liquid-phase catalyst according to claim 1, which is characterized in that the pH adjusting agent is in dilute sulfuric acid or dilute hydrochloric acid
It is one or more.
4. liquid-phase catalyst according to claim 1, which is characterized in that the activator is NaClO, NaClO2And H2O2,
PH adjusting agent is dilute sulfuric acid;The weight content of each component is NaClO 17%, NaClO28.5%, H2O22.5%, H2SO42%.
5. a kind of method for preparing liquid-phase catalyst described in claim 1-4, which is characterized in that
The activator is mixed;
The pH adjusting agent is added in the intermixture using micro-injection pump;
The aqueous solution is added.
6. preparation method according to claim 5, which is characterized in that the addition rate of the pH adjusting agent is 10-20ml/
h。
7. preparation method according to claim 6, which is characterized in that the addition rate of the pH adjusting agent is 10ml/h.
8. a kind of application of liquid-phase catalyst described in claim 1-4, which is characterized in that catalyst is placed in liquid-phase catalyst
The liquid-phase catalyst in liquid-phase catalyst storage tank is delivered to liquid-phase catalyst by liquid-phase catalyst metering force (forcing) pump by storage tank
Grid is sprayed, flue gas enters liquid-phase catalyst injection grid and reacts with the liquid-phase catalyst, and reaction temperature is 65 DEG C -85 DEG C.
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CN201811595315.XA CN109647144A (en) | 2018-12-25 | 2018-12-25 | Liquid phase catalyst, preparation and application |
Applications Claiming Priority (1)
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CN201811595315.XA CN109647144A (en) | 2018-12-25 | 2018-12-25 | Liquid phase catalyst, preparation and application |
Publications (1)
Publication Number | Publication Date |
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CN109647144A true CN109647144A (en) | 2019-04-19 |
Family
ID=66115122
Family Applications (1)
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CN201811595315.XA Pending CN109647144A (en) | 2018-12-25 | 2018-12-25 | Liquid phase catalyst, preparation and application |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110292859A (en) * | 2019-07-23 | 2019-10-01 | 湖北陆盛环保工程有限公司 | A kind of room temperature liquid phase catalytic reduction denitrification apparatus |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110292859A (en) * | 2019-07-23 | 2019-10-01 | 湖北陆盛环保工程有限公司 | A kind of room temperature liquid phase catalytic reduction denitrification apparatus |
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