CN115414781B - Water-based polymer denitration agent and preparation method and application thereof - Google Patents
Water-based polymer denitration agent and preparation method and application thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002861 polymer material Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims description 29
- 239000003814 drug Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 8
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 108010010803 Gelatin Proteins 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 229920000159 gelatin Polymers 0.000 claims description 6
- 239000008273 gelatin Substances 0.000 claims description 6
- 235000019322 gelatine Nutrition 0.000 claims description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 229940015043 glyoxal Drugs 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 241000220479 Acacia Species 0.000 claims description 3
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229940036811 bone meal Drugs 0.000 claims description 2
- 239000002374 bone meal Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229940014259 gelatin Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940032147 starch Drugs 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 32
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010489 acacia gum Nutrition 0.000 description 3
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- 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)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (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)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a water-based polymer denitration agent, a preparation method and application thereof, and belongs to the technical field of denitration agent preparation. The invention discloses a water-based polymer denitration agent which mainly comprises a modified ammonia material, a water-based polymer material, a crosslinking agent and a catalyst. The aqueous polymer denitration agent disclosed by the invention adopts the low-cost aqueous polymer material as the filler, is uniformly mixed with the modified ammonia material, the catalyst and the crosslinking agent, can solve the problems of the existing polymer denitration agent that the solvent is not environment-friendly, the moisture resistance is poor, the blockage is easy, the preparation cost is high and the like, and provides the low-cost environment-friendly moisture-proof aqueous polymer denitration agent which has higher denitration efficiency. In addition, the raw materials of the water-based polymer denitration agent are widely available, cheap and easy to obtain, water is used as a solvent, the prepared denitration agent is safe and environment-friendly, the moisture-proof capacity is excellent, the denitration rate is high, the comprehensive cost is expected to be reduced based on the preparation process of the polymer denitration agent commonly used at present, the water-based polymer denitration agent is produced in a large scale, and the water-based polymer denitration agent can be used as an additive to improve the denitration efficiency of nitrogen oxides (NOx) and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of denitration agents, and relates to a water-based polymer denitration agent, a preparation method and application thereof.
Background
With the increasing environmental protection requirements in recent years, the emission standard of the nitrogen oxides (NO x) in the waste incineration flue gas is more and more strict, and the average value of the emission of part of urban nitrogen oxides (NO x) is even as low as 80mg/Nm 3. Currently, garbage incineration power plants mainly adopt SNCR (selective non-catalytic reduction) and SCR (selective catalytic reduction) technologies to remove nitrogen oxides (NO x). The SNCR adopts urea solution as a reducing agent, the reaction temperature window is 850-1050 ℃, the operation cost of ton garbage is low (about 2 yuan), but the denitration efficiency is about 45 percent, and the requirement of ultralow emission of NO x cannot be met; SCR adopts liquid ammonia or ammonia water and the like as reducing agents, the temperature of a reaction window is 250-450 ℃, the denitration efficiency of more than 80% can be realized by combining the catalytic effect of a catalyst, but the operation cost per ton of garbage is high (about 30-35 yuan), and the catalyst is dangerous waste. Therefore, there is an urgent need to find a new denitration technology with high denitration efficiency and low running cost.
The polymer denitration technology takes modified ammonia as a carrier, polymeric materials such as polymers, catalysts and the like are loaded on the modified ammonia in a polymerization way, a large number of active functional groups such as amino groups, hydroxyl groups and the like are released at high temperature, and the purpose of removing NO x is achieved through catalytic reduction reaction. The polymer denitration technology has the advantages of investment (200 ten thousand yuan is newly added in a 600t/d incineration line), low operation cost (about 10 yuan/ton of garbage) and high denitration efficiency (more than 70 percent), can realize ultra-low emission of NO x, and is the development direction of the NO x deep treatment technology.
The polymer denitration medicament is one of the keys of the polymer catalytic denitration technology, a large number of polymer medicament formula patents have been published in the prior art at present, but part of formula medicaments are powdery materials and are easy to absorb moisture, so that the problem of feeding blockage is easily caused, the polymer materials and solvents thereof used in part of formula are not environment-friendly, and the difficulty of industrial production is high. For example, in China patent 'a denitration agent for denitration of coal-fired flue gas and a preparation method thereof' (patent application number: CN 201810936955.6), methanol is adopted as a solvent, so that the environmental protection is poor; in the Chinese patent 'a high molecular denitration agent and a preparation method thereof' (patent application number: 2016112604891), the polyacrylate adopted is easy to absorb water, which is not beneficial to moisture prevention; in Chinese patent 'a selective macromolecule catalytic denitration agent and application and equipment thereof' (patent application number: CN 201610055201.0), the agent is in a powder state and is easy to block in the transportation and feeding process.
Therefore, the preparation of the environment-friendly and dampproof low-cost polymer denitration agent becomes an important development trend in the field of flue gas denitration.
Disclosure of Invention
Accordingly, one of the objectives of the present invention is to provide an aqueous polymer denitration agent formulation; the second purpose of the invention is to provide a preparation method of the aqueous polymer denitration agent; the invention further aims at the application of the aqueous polymer denitration agent as an additive in the aspect of improving the denitration efficiency of nitrogen oxides (NO x).
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. the aqueous polymer denitration agent comprises a modified ammonia material, an aqueous polymer material, a crosslinking agent and a catalyst;
The modified ammonia material is any one or more of urea, ammonium chloride, ammonium acetate and ammonium carbonate, the aqueous polymer material comprises any one or more of acacia, gelatin, starch, sodium alginate or bone meal, the cross-linking agent comprises any one or more of glutaraldehyde, glyoxal, terephthalaldehyde or terephthalaldehyde, and the catalyst comprises any one or more of carbon powder, manganese dioxide, calcium carbonate, aluminum sulfate, zinc sulfate, manganese sulfate, iron oxide red, magnesium oxide, copper oxide or zinc oxide.
Preferably, the mass ratio of the modified ammonia material to the aqueous polymer material to the cross-linking agent to the catalyst is 500-1000:10-50:1-5:1-3.
2. The preparation method of the aqueous polymer denitration agent comprises the following steps:
(1) Preparation of a polymer suspension I: mixing a water-based high polymer material, a catalyst and water according to the mass ratio of 10-50:1-3:50-250, raising the temperature to 40-50 ℃, and stirring to form a uniformly dispersed suspension I;
(2) Preparing a high molecular suspension II: and (3) cooling the suspension liquid I in the step (1) to 20-40 ℃, adding a cross-linking agent in a stirring state, and stirring for 30-60 min to obtain a polymer suspension liquid II.
(3) Preparing a high molecular denitration agent: and (3) filling the modified ammonia into a medicament coating machine, starting the medicament coating machine to raise the temperature of the modified ammonia to 55-65 ℃, and spraying the polymer suspension II into the medicament coating machine at a rate of 2-5 kg/min for treatment to obtain the denitration agent.
Preferably, in the step (1), the stirring time is 30 to 60 minutes.
Preferably, in the step (3), the treatment time is 30 to 60 minutes.
3. The application of the aqueous polymer denitration agent as an additive in the aspect of improving the denitration efficiency of nitrogen oxides (NO x).
The invention has the beneficial effects that: the invention discloses a water-based polymer denitration agent which mainly comprises a modified ammonia material, a water-based polymer material, a crosslinking agent and a catalyst. The water-based polymer denitration agent disclosed by the invention adopts a low-price environment-friendly water-based polymer material as a filler, is uniformly mixed with a modified ammonia material, a catalyst and a crosslinking agent, can solve the problems of environment-friendliness, poor moisture resistance, easiness in blocking, high production cost and the like of a solvent of the polymer denitration agent in the prior art, and provides the environment-friendly and moisture-proof water-based polymer denitration agent which has higher denitration efficiency. In addition, the raw materials of the water-based polymer denitration agent are easy and convenient to obtain, water is used as a solvent to reduce the material cost, the prepared denitration agent has excellent moisture-proof capability and high denitration rate, and the preparation process based on the conventional polymer denitration agent is expected to reduce the comprehensive cost, is suitable for large-scale production, can be used as an additive to improve the denitration efficiency of nitrogen oxides (NO x), and has wide application prospect.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of an aqueous polymer denitration agent prepared in example 1;
FIG. 2 is a diagram showing a moistureproof mechanism of the aqueous polymer medicament prepared by the invention.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
The preparation method of the aqueous polymer denitration agent comprises the following steps:
(1) Preparation of a polymer suspension I: stirring an aqueous polymer material (Arabic gum), a catalyst (copper oxide) and water according to a mass ratio of 10:1:50 for 30min at 50 ℃ to form a uniformly dispersed polymer suspension I;
(2) Preparing a high molecular suspension II: cooling the polymer suspension I in the step (1) to 30 ℃, continuously maintaining the stirring state, adding a cross-linking agent (terephthalaldehyde, wherein the mass of the cross-linking agent is 10% of that of the water-based polymer material (Arabic gum)) and stirring for 30min to obtain a polymer suspension II;
(3) Preparing an aqueous polymer denitration agent: and (3) loading modified ammonia (urea, wherein the mass ratio of urea to the aqueous polymer material (Arabic gum) is 50:1) into a medicament coating machine, starting the medicament coating machine to raise the temperature of the modified ammonia to 60 ℃, spraying the polymer suspension II into the medicament coating machine at the speed of 2kg/min, and continuously treating for 60min to obtain the aqueous polymer denitration agent.
Example 2
The preparation method of the aqueous polymer denitration agent comprises the following steps:
(1) Preparation of a polymer suspension I: stirring an aqueous polymer material (gelatin), a catalyst (zinc oxide) and a catalyst (carbon powder) with water according to a mass ratio of 20:1:1:100 at 45 ℃ for 30min to form a uniformly dispersed polymer suspension I;
(2) Preparing a high molecular suspension II: cooling the polymer suspension I in the step (1) to 30 ℃, continuously maintaining a stirring state, adding a cross-linking agent (glyoxal, wherein the mass of the cross-linking agent is 10% of that of the water-based polymer material (gelatin)), and stirring for 60min to obtain a polymer suspension II;
(3) Preparing a denitration agent: loading modified ammonia (ammonium acetate, wherein the mass ratio of the ammonium acetate to the aqueous polymer material (gelatin) is 100:1) into a medicament coating machine, starting the medicament coating machine to raise the temperature of the modified ammonia (ammonium acetate) to 60 ℃, spraying the polymer suspension II into the medicament coating machine at the speed of 3kg/min, and continuously treating for 40min to obtain the aqueous polymer denitration agent.
Example 3
The preparation method of the aqueous polymer denitration agent comprises the following steps:
(1) Preparation of a polymer suspension I: stirring an aqueous high polymer material (sodium alginate), a catalyst (iron oxide red) and water according to a mass ratio of 10:1:50 at 40 ℃ for 60min to form a uniformly dispersed high polymer suspension I;
(2) Preparing a high molecular suspension II: cooling the polymer suspension I in the step (1) to 30 ℃, continuously maintaining a stirring state, adding a cross-linking agent (glutaraldehyde, wherein the mass of the cross-linking agent is 10% of that of the water-based polymer material (sodium alginate), and stirring for 60min;
(3) Preparing a denitration agent: loading modified ammonia (ammonium carbonate) into a medicament coating machine, starting the medicament coating machine to raise the temperature of the modified ammonia (ammonium carbonate) to 65 ℃, spraying a polymer suspension II into the medicament coating machine at a rate of 4kg/min, and continuously treating for 30min to obtain the aqueous polymer denitration agent.
Performance testing
FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of an aqueous polymer denitration agent prepared in example 1. As can be seen from FIG. 1, the polymer denitration agent is in solid particles, the modified ammonia material is taken as a core, the polymer, the catalyst and the crosslinking agent are uniformly distributed on the outer surface of the modified ammonia material, a compact coating layer of about 33 mu m is formed, the polymer and the modified ammonia are instantaneously gasified and decomposed in a high temperature state, and react with NOx under the action of the catalyst to generate N 2 and H 2 O, so that the denitration effect is achieved.
FIG. 2 is a diagram showing a moistureproof mechanism of the aqueous polymer denitration agent prepared by the invention. As can be seen from fig. 2, the polymer material and the cross-linking agent undergo a cross-linking reaction on the surface of the modified ammonia material, so that a smooth and compact hydrophobic structure is formed, and the hydrophobic structure can effectively prevent the moisture absorption and hardening of the polymer agent, ensure the fluidity of the polymer agent and ensure the stability of the feeding process.
The aqueous polymer denitration agent prepared in each example is used for treating flue gas, and three parallel experiments are carried out in each example, and three control experiments (only the SNCR system is put into use) are also carried out, wherein the specific process is as follows: the concentration of nitrogen oxides in the discharged flue gas without any treatment is about 350-360 mg/Nm 3, the average temperature of the hearth T1 is about 950 ℃, the aqueous polymer denitration agent prepared according to the embodiment is sprayed in the temperature range of 800-900 ℃, the spraying amount of the agent per ton of garbage is controlled to be 1.2-1.5 kg, the discharge rule of the flue gas NO x is observed, and the result is shown in the table 1.
Table 1 treatment of Smoke with aqueous Polymer denitration Agents of different examples
As can be seen from Table 1, after the aqueous polymer denitration agent prepared in the embodiment of the invention is added into flue gas, the concentration of nitrogen oxide (NO x) in a flue gas emission outlet can be greatly reduced, the denitration efficiency is over 80 percent, and the denitration efficiency is about 45 percent when only SNCR is used, which indicates that the aqueous polymer denitration agent prepared in the invention has higher denitration efficiency.
In addition, the raw materials in the preparation method can be mutually changed and combined, for example, the adopted modified ammonia material can be any one or more of urea, ammonium chloride, ammonium acetate and ammonium carbonate, the polymer material can be any one or more of acacia, gelatin, starch, sodium alginate or bone powder, the cross-linking agent can be any one or more of glutaraldehyde, glyoxal, terephthalaldehyde or terephthalaldehyde, and the catalyst also comprises any one or more of carbon powder, manganese dioxide, calcium carbonate, aluminum sulfate, zinc sulfate, manganese sulfate, iron oxide red, magnesium oxide, copper oxide or zinc oxide. The aqueous polymer denitration agent prepared by the materials has denitration efficiency of more than 85 percent as the products prepared in examples 1 to 3.
In summary, the invention discloses an aqueous polymer denitration agent, which mainly comprises a modified ammonia material, an aqueous polymer material, a crosslinking agent and a catalyst. The aqueous polymer denitration agent disclosed by the invention adopts the low-cost aqueous polymer material as the filler, is uniformly mixed with the modified ammonia material, the catalyst and the crosslinking agent, can solve the problems of environment-friendliness, poor moisture resistance, easiness in blocking, high preparation cost and the like of a solvent of the polymer denitration agent in the existing stage, and provides the environment-friendly moisture-proof aqueous polymer denitration agent which has higher denitration efficiency. In addition, the raw materials of the water-based polymer denitration agent are easy and convenient to obtain, water is used as a solvent to reduce the material cost, the prepared denitration agent has excellent moisture-proof capability and high denitration rate, and the preparation process based on the conventional polymer denitration agent is expected to reduce the comprehensive cost, is suitable for large-scale production, can be used as an additive to improve the denitration efficiency of nitrogen oxides (NO x), and has wide application prospect.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (3)
1. The preparation method of the aqueous polymer denitration agent is characterized by comprising the following steps of:
(1) Preparation of a polymer suspension I: mixing a water-based high polymer material, a catalyst and water according to the mass ratio of 10-50:1-3:50-250, raising the temperature to 40-50 ℃, and stirring to form a uniformly dispersed suspension I;
(2) Preparing a high molecular suspension II: cooling the suspension I in the step (1) to 20-40 ℃, adding a cross-linking agent in a stirring state, and stirring for 30-60 min to obtain a high polymer suspension II;
(3) Preparing a high molecular denitration agent: filling the modified ammonia material into a medicament coating machine, starting the medicament coating machine to raise the temperature of the modified ammonia to 55-65 ℃, and spraying the polymer suspension II into the medicament coating machine at a rate of 2-5 kg/min for treatment to obtain the denitration agent;
The modified ammonia material is any one or more of urea, ammonium chloride, ammonium acetate and ammonium carbonate, the aqueous polymer material comprises any one or more of acacia, gelatin, starch, sodium alginate or bone meal, the cross-linking agent comprises any one or more of glutaraldehyde, glyoxal, terephthalaldehyde or terephthalaldehyde, and the catalyst comprises any one or more of carbon powder, manganese dioxide, calcium carbonate, aluminum sulfate, zinc sulfate, manganese sulfate, iron oxide red, magnesium oxide, copper oxide or zinc oxide;
The mass ratio of the modified ammonia material to the water-based polymer material to the cross-linking agent to the catalyst is 500-1000:10-50:1-5:1-3.
2. The method according to claim 1, wherein in the step (1), the stirring time is 30 to 60 minutes.
3. The method according to claim 1, wherein in the step (3), the treatment time is 30 to 60 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105396594A (en) * | 2015-11-04 | 2016-03-16 | 雷春生 | Preparation method of low-temperature simultaneous desulfurization and denitration catalyst |
| CN106621782A (en) * | 2016-12-30 | 2017-05-10 | 深圳市唯有新材料有限公司 | High-polymer denitration agent and preparation method thereof |
| WO2017121022A1 (en) * | 2016-01-12 | 2017-07-20 | 北京化工大学 | Integrated purification method and system for industrial waste gas containing cyanides, hydrocarbons and nox |
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| CN102319559B (en) * | 2011-06-03 | 2013-07-31 | 中国科学院过程工程研究所 | Surface deposition honeycomb flue gas denitration catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105396594A (en) * | 2015-11-04 | 2016-03-16 | 雷春生 | Preparation method of low-temperature simultaneous desulfurization and denitration catalyst |
| WO2017121022A1 (en) * | 2016-01-12 | 2017-07-20 | 北京化工大学 | Integrated purification method and system for industrial waste gas containing cyanides, hydrocarbons and nox |
| CN106621782A (en) * | 2016-12-30 | 2017-05-10 | 深圳市唯有新材料有限公司 | High-polymer denitration agent and preparation method thereof |
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