CN114669179A - Composite organic denitration agent and preparation method thereof - Google Patents
Composite organic denitration agent and preparation method thereof Download PDFInfo
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- CN114669179A CN114669179A CN202210195737.8A CN202210195737A CN114669179A CN 114669179 A CN114669179 A CN 114669179A CN 202210195737 A CN202210195737 A CN 202210195737A CN 114669179 A CN114669179 A CN 114669179A
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- Prior art keywords
- denitration agent
- denitration
- composite organic
- agent
- uniformly stirring
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- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000003063 flame retardant Substances 0.000 claims abstract description 8
- 239000006172 buffering agent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003337 fertilizer Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000003631 expected effect Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
-
- 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
- B01D53/14—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 by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
Abstract
The invention discloses a composite organic denitration agent and a preparation method thereof, relating to the technical field of denitration and comprising 50-90% of an active organic mixture, 2-7% of a flame retardant, 1-3% of an emulsifier, 0.1-1% of a buffering agent and 1-5% of a synergist. The method adopts an active organic mixture as a main raw material, does not contain ammonia, does not generate ammonia escape, and has the characteristics of high denitration efficiency, wide applicable temperature range, safety and environmental protection.
Description
Technical Field
The invention relates to the technical field of denitration, and particularly relates to a composite organic denitration agent and a preparation method thereof.
Background
Nitrogen Oxides (NO)X) Is one of three main atmospheric pollutants (smoke dust, sulfur dioxide and nitrogen oxide), and has a wider harm degree than sulfur dioxide. With the development of economy and the improvement of environmental protection requirements, the air pollution caused by the effective control of the emission of various boilers and kiln flue gases is not slow enough, and particularly, the nitrogen oxides in the combustion flue gases are removed to prevent the environmental pollution, so that the problem in the world is pointed out.
The SNCR denitration system of the existing cement kiln, glass kiln, gas, coal and biomass boiler has the defects of low denitration efficiency and difficulty in reaching NO X≤50mg/Nm3The problem of ultralow emission standard, SCR deNOx systems use cost height in addition, and the catalyst life-span is short, can't realize the low-load denitration again.
Disclosure of Invention
Aiming at the technical problems, the invention overcomes the defects of the prior art and provides a composite organic denitration agent which comprises 50-90% of an active organic mixture, 2-7% of a flame retardant, 1-3% of an emulsifier, 0.1-1% of a buffering agent and 1-5% of a synergist.
The technical scheme of the invention is further defined as follows:
the composite organic denitration agent is prepared by mixing an active organic mixture of a biological liquid fertilizer, NaOH, biochar and propyl butyrate according to the proportion of 5:2:1: 2.
The composite organic denitration agent mainly comprises tris (2-chloroethyl) phosphate as a flame retardant.
The emulsifier of the composite organic denitration agent mainly comprises Tween 80.
In the composite organic denitration agent, the buffering agent mainly comprises sodium citrate.
The composite organic denitration agent mainly comprises sodium oxalate as a synergist.
The invention also aims to provide a preparation method of the composite organic denitration agent, which comprises the following specific steps:
s1, adding NaOH into water, uniformly stirring, adding the biological liquid fertilizer, continuously stirring for dissolving, adding biochar and propyl butyrate, and continuously stirring until the biochar and the propyl butyrate are completely dissolved to obtain an active organic mixture;
S2, adding a flame retardant into the prepared active organic mixture, and uniformly stirring;
s3, adding an emulsifier, and uniformly stirring;
s4, adding a buffering agent, and uniformly stirring;
and S5, adding the synergist, and uniformly stirring to obtain the composite organic denitration agent.
The invention has the beneficial effects that: an ammonia-free organic denitration mode is adopted, so that the method is environment-friendly and operates without ammonia, and the adverse effect of free ammonia is avoided from the source; the safety problem of liquid ammonia storage does not exist; when the boiler operates at low load, the flue gas can also realize ultralow emission. Has the advantages of high denitration efficiency, simple installation, low investment equivalent to SNCR, lower operating cost than SCR denitration process, and capability of meeting the requirement of NO in a unit full-load stateX≤50mg/Nm3Ultra low emission standard requirements.
Detailed Description
The composite organic denitration agent and the preparation method thereof provided by the embodiment comprise the following specific steps:
s1, adding 2 g of NaOH into 75 g of water, uniformly stirring the mixture manually or mechanically, adding 5 g of biological liquid fertilizer, continuously stirring the mixture for dissolution, adding 1 g of powdered biochar (200 meshes) and 2 g of propyl butyrate, and continuously stirring the mixture until the biochar and the propyl butyrate are completely dissolved to obtain an active organic mixture;
s2, adding 2 g of flame retardant with the main component of tris (2-chloroethyl) phosphate sold in the market into the prepared active organic mixture, and uniformly stirring by manpower or machinery;
S3, adding 2 g of emulsifier which is commercially available Tween80 as a main component, and uniformly stirring by manpower or machinery;
s4, adding 0.2 g of buffering agent which is commercially available and mainly comprises sodium citrate, and uniformly stirring by manpower or machinery;
s5, adding 3 g of synergist which is commercially available and mainly comprises sodium oxalate, and uniformly stirring the mixture manually or mechanically to obtain the composite organic denitration agent.
The test is carried out on a 60t/h gas boiler in a certain steel mill, and the expected effect is achieved. The boiler adopts blast furnace gas and coke oven gas as fuel, adopts SNCR denitration mode, adopts 20% ammonia water as denitration agent, two spray guns are respectively arranged at two sides of furnace chamber, and initial NO isXAnd the content is less than 50mg/Nm in long-term cultivation, and the denitration device is basically in an off-state. In order to achieve the expected effect, the fuel ratio of the boiler is adjusted, the coke oven gas ratio is increased, and the initial NO is addedXRegulating the content to 80-100mg/Nm, adopting a ton barrel shape in the test, utilizing the existing SNCR denitration device by a pump and a spray gun, and specifically carrying out flue gas parameters as follows:
TABLE 1 boiler flue gas Current parameters
| Item | Unit of | Parameter(s) | Remarks for note |
| Boiler scale | 60t/h | ||
| Furnace shape | Gas boiler | ||
| Fuel | Boiler gas, coke oven gas | ||
| Flue gas volume (maximum) | Nm3/h | 90000 | |
| Furnace smoke temperature | ℃ | 800-900 | |
| NOXInitial concentration | mg/m3 | 80-100 | |
| Oxygen content | % | ≤3 |
After the denitration agent is added, the flue gas parameters are as follows:
TABLE 2 flue gas parameters after denitration
| Item | Unit of | Parameter(s) | Remarks for note |
| Furnace smoke temperature | ℃ | 800-900 | |
| NOXConcentration after purification | mg/m3 | 30-50 | Stabilization time of 30min |
| NOXMinimum concentration | mg/m3 | 15-20 | Increasing the dosage of the denitrifier, and stabilizing for 10min |
| Consumption of denitration agent | Kg/h | 70-100 | The limit consumption is 150Kg/h |
| Denitration efficiency | % | 50-85 | |
| Expected effect | To achieve |
As can be seen from the table, the denitration agent disclosed by the invention can achieve higher denitration efficiency, and the expected effect is obvious. The limit consumption in the table means that the dosage of the denitrifier is increased, NOXDenitration agent consumption during ethanol drainage concentration < 20 mg/Nm. By adjusting the load of the boiler, when the temperature of the hearth is between 700 ℃ and 800 ℃, NOXThe discharge concentration can also be guaranteed to be stable below 50 mg/Nm.
Compared with the prior art, the method adopts the active organic mixture as the main raw material, does not contain ammonia, does not generate ammonia escape, and has the characteristics of high denitration efficiency, wide applicable temperature range, safety and environmental protection.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (7)
1. A composite organic denitration agent is characterized in that: comprises 50-90% of active organic mixture, 2-7% of flame retardant, 1-3% of emulsifier, 0.1-1% of buffering agent and 1-5% of synergist.
2. The composite organic denitration agent of claim 1, which is characterized in that: the active organic mixture is prepared by mixing biological liquid fertilizer, NaOH, biochar and propyl butyrate according to the proportion of 5:2:1: 2.
3. The composite organic denitration agent of claim 1, which is characterized in that: the flame retardant mainly comprises tris (2-chloroethyl) phosphate.
4. The composite organic denitration agent of claim 1, wherein: the emulsifier mainly comprises Tween 80.
5. The composite organic denitration agent of claim 1, wherein: the buffer mainly comprises sodium citrate.
6. The composite organic denitration agent of claim 1, wherein: the synergist mainly comprises sodium oxalate.
7. A preparation method of a composite organic denitration agent is characterized by comprising the following steps: the method is applied to any one of claims 1 to 5, and comprises the following specific steps:
s1, adding NaOH into water, uniformly stirring, adding the biological liquid fertilizer, continuously stirring for dissolving, adding biochar and propyl butyrate, and continuously stirring until the biochar and the propyl butyrate are completely dissolved to obtain an active organic mixture;
s2, adding a flame retardant into the prepared active organic mixture, and uniformly stirring;
S3, adding an emulsifier, and uniformly stirring;
s4, adding a buffering agent, and uniformly stirring;
s5, adding the synergist, and uniformly stirring to obtain the composite organic denitration agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210195737.8A CN114669179A (en) | 2022-03-02 | 2022-03-02 | Composite organic denitration agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210195737.8A CN114669179A (en) | 2022-03-02 | 2022-03-02 | Composite organic denitration agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114669179A true CN114669179A (en) | 2022-06-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210195737.8A Pending CN114669179A (en) | 2022-03-02 | 2022-03-02 | Composite organic denitration agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114669179A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115253625A (en) * | 2022-08-17 | 2022-11-01 | 上海全熙环保科技股份有限公司 | Efficient solid denitration agent and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817282A (en) * | 1996-03-28 | 1998-10-06 | Dynamotive Technologies Corporation | Reduction of nitrogen oxides |
| US20180043302A1 (en) * | 2015-03-20 | 2018-02-15 | Yongfeng Boyuan Industry Co. Ltd., Jiangxi Province | Desulfurization and denitration agent |
| CN110433788A (en) * | 2019-08-05 | 2019-11-12 | 龙净科杰环保技术（上海）有限公司 | Using biomass-based active carbon as denitrating catalyst of carrier and preparation method thereof |
| CN111167277A (en) * | 2020-01-19 | 2020-05-19 | 山东省昔利环境科技有限公司 | Preparation method of composite organic calcium-based denitration agent |
| CN111514738A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration water agent for dry-process cement kiln, use method of composite biomass denitration water agent and denitration system |
| CN111514726A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration agent for dry-process cement kiln, use method of denitration agent and denitration system |
| CN112354343A (en) * | 2020-10-12 | 2021-02-12 | 山东奥淼科技发展有限公司 | Ammonia-free organic liquid denitration agent and preparation method thereof |
| CN113117475A (en) * | 2021-04-30 | 2021-07-16 | 山东省昔利环境科技有限公司 | Composite fiber denitration agent and preparation method thereof |
-
2022
- 2022-03-02 CN CN202210195737.8A patent/CN114669179A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817282A (en) * | 1996-03-28 | 1998-10-06 | Dynamotive Technologies Corporation | Reduction of nitrogen oxides |
| US20180043302A1 (en) * | 2015-03-20 | 2018-02-15 | Yongfeng Boyuan Industry Co. Ltd., Jiangxi Province | Desulfurization and denitration agent |
| CN111514738A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration water agent for dry-process cement kiln, use method of composite biomass denitration water agent and denitration system |
| CN111514726A (en) * | 2019-02-02 | 2020-08-11 | 广东万引科技发展有限公司 | Novel composite biomass denitration agent for dry-process cement kiln, use method of denitration agent and denitration system |
| CN110433788A (en) * | 2019-08-05 | 2019-11-12 | 龙净科杰环保技术（上海）有限公司 | Using biomass-based active carbon as denitrating catalyst of carrier and preparation method thereof |
| CN111167277A (en) * | 2020-01-19 | 2020-05-19 | 山东省昔利环境科技有限公司 | Preparation method of composite organic calcium-based denitration agent |
| CN112354343A (en) * | 2020-10-12 | 2021-02-12 | 山东奥淼科技发展有限公司 | Ammonia-free organic liquid denitration agent and preparation method thereof |
| CN113117475A (en) * | 2021-04-30 | 2021-07-16 | 山东省昔利环境科技有限公司 | Composite fiber denitration agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115253625A (en) * | 2022-08-17 | 2022-11-01 | 上海全熙环保科技股份有限公司 | Efficient solid denitration agent and preparation method thereof |
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