CN107115773A - A kind of Modified Urea denitrfying agent and preparation method thereof - Google Patents
A kind of Modified Urea denitrfying agent and preparation method thereof Download PDFInfo
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- CN107115773A CN107115773A CN201710484224.8A CN201710484224A CN107115773A CN 107115773 A CN107115773 A CN 107115773A CN 201710484224 A CN201710484224 A CN 201710484224A CN 107115773 A CN107115773 A CN 107115773A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
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- B01D2251/21—Organic compounds not provided for in groups B01D2251/206 or B01D2251/208
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
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- 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
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- 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
- B01D2258/0233—Other waste gases from cement factories
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
It is used for Modified Urea denitrfying agent the invention discloses one kind, composition is made up of three parts：The urea that (1) 100.0 mass parts are；The macromolecules such as polyethylene glycol, polyacrylic acid, Sodium Polyacrylate, the polyvinyl alcohol of (2) 0.5~10.0 mass parts；The modified component of (3) 0.1~10.0 mass parts.Modified component is to support titanyl sulfate or titanyl sulfate and zinc sulfate and/or the silica micro-capsule of manganese sulfate and/or aluminum sulfate.This denitrfying agent denitration rate under the conditions of 750~1050 DEG C can reach 83.2%~99.0%.Composite denitration agent preparation method is simple, can be extensively using the high-temperature gas denitration such as steam power plant, garbage burning factory.
Description
Technical field
It is used for the Modified Urea denitrfying agent of boiler gas or denitrating flue gas the present invention relates to a kind of.
Background technology
At present, the standard that China discharges to industrial tail gas is more and more stricter.NO in stationary source industrial waste gasXParticularly by
Pay attention to.The typical method for administering NOx is carried out based on SNCR reaction (SNCR), SNCR denitration technology
Core content is：In the case where no catalyst is participated in, with reducing agents such as ammonia or urea by the NO in flue gasXIt is reduced to nitrogen
And water.The topmost advantage of SNCR denitration system is that construction is that one-time investment and operating cost are all relatively low, and equipment is taken up an area
Area is smaller, at present, and SNCR denitration technology is in China's coal-fired plant flue gas denitration technology.SNCR operating temperature is general 950
DEG C~1050 DEG C of temperature ranges, the reduction of SNCR denitration efficiency can be caused by being typically due to temperature fluctuation：Temperature is too low, ammonia or urea
NOx activity decrease is reduced, temperature is too high, causes ammonia or urea to be oxidized to NOx.Therefore, widen using urea or ammonia as
The operating temperature of the denitration of raw material, adapting it to more denitrating flue gas operating modes has very important value.
The content of the invention
It is an object of the invention to provide a kind of Modified Urea denitrfying agent.The technical solution used in the present invention is：
One kind is used for Modified Urea denitrfying agent,
(1) Modified Urea denitrfying agent, it is made up of the following raw material：100.0 the urea of mass parts；0.5~10 mass parts
High molecular component；The modified component of 0.1~10.0 mass parts, 0.001~0.5 building component.High molecular component is at least to contain
A kind of following additive of composition：Polyethylene glycol, polyacrylic acid, Sodium Polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone；Change
Property component be at least containing a kind of following additive of composition：Ammonium stearate, magnesium stearate, calcium stearate, mould inhibitor, the precipitation method
Calcium carbonate, magnesia, zeolite；Building component is the silicon oxide vesicle for being loaded with metal oxide.
Further, described metal sulfate, metallic element therein is in titanium or titanium and at least following element
It is a kind of：Manganese, zinc, aluminium.
Described silicon oxide vesicle preparation method is as follows：Under the conditions of at room temperature, by the cocounut oil of 0.8~1.5 mass parts
Base Sodium Glycinate and 0.5~1.0 part of lauryl sodium sulfate are dissolved in the water of 100.0 mass parts, add 1.0~1.9 mass
The mass percent concentration of part is 1-20.0% phosphate aqueous solution, is stirred, hereafter, and it is 8.0~12.0 to add mass parts
Silicon source, continue stir, product is filtered out, in 25-50 DEG C of drying, the silicon oxide vesicle of phosphorylation is obtained.
Further, described silicon source is one or more kinds of mixtures in tetraethyl orthosilicate, Ludox, sodium metasilicate.
The preparation method of described building component is as follows：The mass parts of silicon oxide vesicle 100 of the phosphorylation of preparation are added
Stirred in the aqueous solution for entering the metal salt that the mass percent concentration for being 1000 to mass parts is 1-15.0% (preferably 15%)
After mixing, dried under the conditions of 25-50 DEG C (preferably 50 DEG C), obtain building component.By building component by nitric acid dousing, and it is dilute
Release, centrifuge, determining molten, using inductance coupling plasma emissioning spectral analysis metal ion in solution content, determining building component
Middle metal ion content.
Further, described metal salt solution is：One kind in titanyl sulfate, zinc sulfate, manganese sulfate, aluminum sulfate or
A variety of mixtures.
A kind of Modified Urea denitrfying agent, its preparation method is：It is 100 by mass ratio：(0.5~10)：(0.1~10.0)：
Urea, high molecular component, modified component and the building component of (0.001~0.5) are compounded, while being stirred, wherein stirring
It is the meter per second of 40 meter per seconds~80 to mix oar linear velocity, and mixing time is 5~10 minutes, obtains powder end-product.
(2) out of stock efficiency is higher：This Modified Urea denitrfying agent can be used for denitrating flue gas, be taken off with higher
Nitre rate：Denitration rate can reach 83.2%~99.0% under the conditions of 750~1050 DEG C.
The present invention provides a kind of novel Modified Urea denitrfying agent,：1. out of stock dose using urea as main component, out of stock dose of tool
There is SNCR inexpensive feature；2. the building component that vesica is supported, not only increases reactivity and has widened operating temperature,
So that out of stock adaptive temperature scope is substantially widened to 750~1050 DEG C, denitration reaction activity increase causes out of stock efficiency obvious
Improve to 83.2%~99.0%；3. the occupation area of equipment used is small, maintenance and the cost of overhaul are relatively low, equipment noise is small,
Stable, this technology is applied to the denitrating techniques such as thermal power generation, cement plant, chemical plant, is with a wide range of applications.
Embodiment
Embodiment 1
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate of 1.5 mass parts and 0.5 part
Lauryl sodium sulfate is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent concentration of 1.0 mass parts
20.0%), to stir.Hereafter, the tetraethyl orthosilicate that mass parts are 8.0 is added.Continue after stirring 20 minutes, product is filtered
Go out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the matter of silicon oxide vesicle 100.0 of phosphorylation
Amount part is added to the aqueous solution for the titanyl sulfate that mass parts are 1000 (wherein：Mass percent concentration to stir in 15.0%)
After 20 minutes, filter out in being dried under 50 degrees celsius, obtain building component A.Titanium element constituent content is：2.3%.
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 30000) of 0.5 mass parts, 5.0 mass parts
Sodium A molecular sieves, 0.001 mass parts building component A is compounded, and is mixed by homogenizer.Reaction condition is：Stirring
Oar linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 1#.
2) denitrification test：
Denitration performance is tested：Before denitration effect experiment, manufacture experimental rig (containing 750-1050 DEG C of reactor, NO steel cylinders and
Enter exhanst gas outlet pipeline in reactor pipeline system, denitrfying agent feed bin and the double helix feed system for entering reactor, reactor,
Flue gas analyzer).
A. NO steel cylinders are opened, flow velocity 5L/min, in reactor exhanst gas outlet pipeline cigarette receiving qi leel analyzer, surveys NO concentration；
B. after flue gas analyzer NO concentration is stable, macromolecule denitrfying agent is added, flow 5g/min surveys NO concentration；
C. according to NO concentration twice, denitration efficiency is calculated.
It the results are shown in Table 1.
Embodiment 2
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate of 1.5 mass parts and 0.6 part
Lauryl sodium sulfate is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent concentration of 1.9 mass parts
20.0%), to stir.Hereafter, the tetraethyl orthosilicate that mass parts are 12.0 is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the matter of silicon oxide vesicle 100 of phosphorylation
Amount part is added to the aqueous solution for the metal salt that mass parts are 1000 (wherein：The mass percent concentration of titanyl sulfate is 1.0%；
The mass percent concentration of zinc sulfate is 13.0%；After the mass percent concentration of manganese sulfate is stirring in 1.0%) 20 minutes,
Filter out in being dried under 50 degrees celsius, obtain building component B.Titanium elements content is：0.2%；Zn-ef ficiency content is：1.6%；
Manganese element content is：0.3%.
Step 2：The urea of 100.0 mass parts, 0.5 mass parts polyacrylic acid, 5.0 mass parts magnesia, 0.2 mass parts
Building component B is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is 40 meter per second~80
Meter per second, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 2#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 3
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate of 1.0 mass parts and 0.8 part
Lauryl sodium sulfate is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent concentration of 1.5 mass parts
20.0%), to stir.Hereafter, the tetraethyl orthosilicate that mass parts are 10.0 is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the matter of silicon oxide vesicle 100 of phosphorylation
Amount part is added to the aqueous solution for the metal salt that mass parts are 1000 (wherein：The mass percent concentration of titanyl sulfate is 2.2%；
After the mass percent concentration of manganese sulfate is stirring in 12.8%) 20 minutes, filter out in being dried under 50 degrees celsius, increased
Imitate component C.Titanium elements content is：0.5%；Manganese element content is：1.3%.
Step 2：The urea of 100.0 mass parts, 0.5 mass parts Sodium Polyacrylate, 5.0 mass parts calcium stearates, 0.25 matter
Amount part building component C is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is 40 meter per seconds
~80 meter per seconds, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 3#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 4
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.5 mass of 1.0 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.2 mass parts
Concentration is 20.0%), to stir.Hereafter, the sodium metasilicate of 3.0 mass parts and the tetraethyl orthosilicate of 5.0 mass parts are added.Continue
After stirring 20 minutes, product is filtered out, in being dried under 50 degrees celsius, the silicon oxide vesicle of phosphorylation is obtained.By 100 mass
The silicon oxide vesicle of part phosphorylation is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate quality percentage
Specific concentration is 1.2%；After aluminum sulfate mass percent concentration is stirring in 13.8%) 20 minutes, filter out in 50 degrees celsius
Lower drying, obtains building component D.Titanium elements content is：0.2%.
Step 2：The urea of 100.0 mass parts, the polyvinyl alcohol of 0.5 mass parts, the calcium stearate of 5.0 mass parts, 0.25
Mass parts building component D is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity be 40 meters/
Second~80 meter per seconds, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 4#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 5
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.8 mass of 0.8 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.4 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 9.5 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 10.0%；Sulfuric acid
After zinc mass percent concentration is stirring in 5.0%) 20 minutes, filter out in being dried under 50 degrees celsius, obtain building component
E.Titanium elements content is：1.4%；Zn-ef ficiency content is：0.5%.
Step 2：The urea of 100.0 mass parts, the polyvinylpyrrolidone of 0.5 mass parts, the stearic acid of 5.0 mass parts
Magnesium, 0.32 mass parts building component E is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity
For the meter per second of 40 meter per seconds~80, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 4#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 6
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.5 mass of 0.8 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.3 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 11.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 1.0%；Sulphur
Sour zinc mass percent concentration is 5.0%；Manganese sulfate mass percent concentration is 8.0%；Aluminum sulfate mass percent concentration is
1.0%) after being stirred 20 minutes in, filter out in being dried under 50 degrees celsius, obtain building component F.Titanium elements content is：
0.2%；Zn-ef ficiency content is：0.4%；Manganese element content is：1.0%；Aluminium element content is：0.2%
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 25000) of 10.0 mass parts, 5.0 mass
The ammonium stearate of part, 0.50 mass parts building component F is compounded, mixed by homogenizer.Reaction condition is：Stir
It is the meter per second of 40 meter per seconds~80 to mix oar linear velocity, and mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 6#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 7
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.6 mass of 0.8 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.9 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 10.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 1.0%；Sulphur
Sour manganese mass percent concentration is 3.9%；After aluminum sulfate mass percent concentration is stirring in 10.0%) 20 minutes, filter out in
Dried under 50 degrees celsius, obtain building component G.Titanium elements content is：0.2%；Manganese element content is：0.6%；Aluminium element
Content is：1.2%.
Step 2：The urea of 100.0 mass parts, the polyacrylic acid of 10.0 mass parts, the ammonium stearate of 2.0 mass parts, 2.0
The magnesium stearate of mass parts, the calcium stearate of 2.0 mass parts, the magnesia of 2.0 mass parts, the NaA zeolites of 2.0 mass parts,
0.05 mass parts building component F is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is
The meter per second of 40 meter per seconds~80, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 7#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 8
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.7 mass of 1.2 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.8 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 12.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 5.5%；Sulphur
Sour zinc mass percent concentration 2.5%；Manganese sulfate mass percent concentration 2.0%；Aluminum sulfate mass percent concentration is
5.0%) after being stirred 20 minutes in, filter out in being dried under 50 degrees celsius, obtain building component H.Titanium elements content is：
0.5%；Zn-ef ficiency content is：0.6%；Manganese element content is：0.4%；Aluminium element content is：0.5%.
Step 2：The urea of 100.0 mass parts, the Sodium Polyacrylate of 10.0 mass parts, the ammonium stearate of 10.0 mass parts,
0.15 mass parts building component H is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is
The meter per second of 40 meter per seconds~80, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 8#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 9
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.9 mass of 1.2 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.0 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 10.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 3.2%；Sulphur
Sour zinc mass percent concentration 10.0%；Manganese sulfate mass percent concentration 1.8%) in stirring 20 minutes after, filter out and taken the photograph in 50
Dried under the conditions of family name's degree, obtain building component I.Titanium elements content is：0.5%；Zn-ef ficiency content is：1.3%；Manganese element content
For：0.3%.
Step 2：The urea of 100.0 mass parts, the polyvinyl alcohol of 10.0 mass parts, the magnesium stearate of 10.0 mass parts,
0.32 mass parts building component I is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is
The meter per second of 40 meter per seconds~80, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 9#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 10
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 1.0 mass of 1.2 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.0 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 10.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 3.5%；Sulphur
Sour zinc mass percent concentration 3.2%；Manganese sulfate mass percent concentration 5.8%；Aluminum sulfate mass percent concentration is
2.5%) after being stirred 20 minutes in, filter out in being dried under 50 degrees celsius, obtain building component J.
Step 2：The urea of 100.0 mass parts, the polypyrrole alkanone of 10.0 mass parts, the calcium stearate of 10.0 mass parts,
0.15 mass parts building component H is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is
The meter per second of 40 meter per seconds~80, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 10#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 11
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.8 mass of 1.0 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.0 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 8.9 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 85.5%；Sulfuric acid
Zinc mass percent concentration 1.3%；Manganese sulfate mass percent concentration 2.6%；2.6%) aluminum sulfate mass percent concentration is
After middle stirring 20 minutes, filter out in being dried under 50 degrees celsius, obtain building component K.Titanium elements content is：1.0%；Zinc member
Cellulose content is：0.2%；Manganese element content is：0.6%；Aluminium element content is：0.6%.
Step 2：The urea of 100.0 mass parts, the polyvinyl alcohol of 7.0 mass parts, the calcium carbonate of 10.0 mass parts, 0.39
Mass parts building component K is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity be 40 meters/
Second~80 meter per seconds, mixing time is 5~10 minutes, obtains powder end-product, sample is designated as 11#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 12
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.6 mass of 1.0 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.2 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 11.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 1.3%；Sulphur
Sour zinc mass percent concentration 2.5%；Manganese sulfate mass percent concentration 2.2%；Aluminum sulfate mass percent concentration is
9.0%) after being stirred 20 minutes in, filter out in being dried under 50 degrees celsius, obtain building component L.Titanium elements content is：
0.2%；Zn-ef ficiency content is：0.6%；Manganese element content is：0.4%；Aluminium element content is：1.1%
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight 20000) of 7.0 mass parts, 10.0 mass parts
Magnesia, 0.42 mass parts building component H compounded, mixed by homogenizer.Reaction condition is：Agitating paddle
Linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder end-product, sample is designated as 12#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 13
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.5 mass of 1.1 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.3 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 8.5 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 1.3%；Sulfuric acid
Zinc mass percent concentration 2.4%；Manganese sulfate mass percent concentration 4.5%；6.8%) aluminum sulfate mass percent concentration is
After middle stirring 20 minutes, filter out in being dried under 50 degrees celsius, obtain building component M.Titanium elements content is：0.2%；Zinc member
Cellulose content is：0.6%；Manganese element content is：0.5%；Aluminium element content is：0.6%
Step 2：The urea of 100.0 mass parts, the Sodium Polyacrylate of 7.0 mass parts, the sodium A zeolites of 10.0 mass parts,
0.15 mass parts building component M is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is
The meter per second of 40 meter per seconds~80, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 13#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 14
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.6 mass of 1.2 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.5 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 9.5 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 3.6%；Sulfuric acid
Zinc mass percent concentration 3.5%；Manganese sulfate mass percent concentration 3.2%；4.7%) aluminum sulfate mass percent concentration is
After middle stirring 20 minutes, filter out in being dried under 50 degrees celsius, obtain building component N.Titanium elements content is：0.5%；Zinc member
Cellulose content is：0.7%；Manganese element content is：0.5%；Aluminium element content is：0.4%
Step 2：The urea of 100.0 mass parts, the polyvinyl alcohol of 10.0 mass parts, the sodium A zeolites of 0.1 mass parts, 0.50
Mass parts building component N is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity be 40 meters/
Second~80 meter per seconds, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 14#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 15
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.6 mass of 1.3 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.9 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 11.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 1.5%；Sulphur
Sour zinc mass percent concentration 3.7%；Manganese sulfate mass percent concentration 3.2%；Aluminum sulfate mass percent concentration is
6.6%) after being stirred 20 minutes in, filter out in being dried under 50 degrees celsius, obtain building component O.Titanium elements content is：
0.2%；Zn-ef ficiency content is：0.6%；Manganese element content is：0.5%；Aluminium element content is：0.5%.
Step 2：The urea of 100.0 mass parts, the polypyrrole alkanone of 7.0 mass parts, 0.1 magnesia, 0.28 mass parts increase
Effect component O is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is 40 meter per second~80
Meter per second, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 15#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 16
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.7 mass of 1.4 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.4 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 10.0 mass parts is added.Continue after stirring 20 minutes, will produce
Thing is filtered out, and in being dried under 50 degrees celsius, obtains the silicon oxide vesicle of phosphorylation.By the titanium dioxide of 100 mass parts phosphorylations
Silicon vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 5.6%；Sulphur
Sour zinc mass percent concentration 3.3%；Manganese sulfate mass percent concentration 2.6%；Aluminum sulfate mass percent concentration is
3.5%) after being stirred 20 minutes in, filter out in being dried under 50 degrees celsius, obtain building component P.Titanium elements content is：
0.5%；Zn-ef ficiency content is：0.7%；Manganese element content is：0.6%；Aluminium element content is：0.7%.
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight 15000) of 2.0 mass parts, 1.5 mass parts
Polyacrylic acid, the Sodium Polyacrylate of 0.5 mass parts, the polyvinyl alcohol of 1.5 mass parts, the polyvinylpyrrolidone of 0.5 mass parts,
The calcium carbonate of 0.1 mass parts, 0.5 mass parts building component P is compounded, and is mixed by homogenizer.Reaction condition
For：Agitating paddle linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as
8#。
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 17
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 1.0 mass of 1.1 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.2 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 8.2 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 5.7%；Sulfuric acid
Zinc mass percent concentration 1.4%；Manganese sulfate mass percent concentration 3.3%；4.6%) aluminum sulfate mass percent concentration is
After middle stirring 20 minutes, filter out in being dried under 50 degrees celsius, obtain building component Q.Titanium elements content is：0.5%；Zinc member
Cellulose content is：0.3%；Manganese element content is：0.5%；Aluminium element content is：0.4%.
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 15000) of 2.0 mass parts, mass parts are
1.0 polyacrylic acid, the calcium stearate of 0.1 mass parts, 0.35 mass parts building component Q is compounded, and passes through homogenizer
Mixed.Reaction condition is：Agitating paddle linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder
Last end-product.Sample is designated as 17#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 18
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 0.9 mass of 0.9 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.0 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 8.9 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 2.6%；Sulfuric acid
Zinc mass percent concentration 1.6%；After manganese sulfate mass percent concentration is stirring in 2.5%) 20 minutes, filter out Celsius in 50
Dried under the conditions of degree, obtain building component R.Titanium elements content is：0.4%；Zn-ef ficiency content is：0.3%；Manganese element content
For：0.6%.
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 15000) of 7.0 mass parts, mass parts are
1.0 polyacrylic acid, mass parts are 0.5 Sodium Polyacrylate, the magnesium stearate of 0.1 mass parts, 0.5 mass parts building component Q
Compounded, mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is the meter per second of 40 meter per seconds~80, is stirred
The time is mixed for 5~10 minutes, powder end-product is obtained.Sample is designated as 18#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 19
1) Modified Urea denitrfying agent is prepared：
Step one：Prepare synergist：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate and 1.0 mass of 0.8 mass parts
The lauryl sodium sulfate of part is dissolved in the water of 100.0 mass parts, adds the phosphate aqueous solution (mass percent of 1.0 mass parts
Concentration is 20.0%), to stir.Hereafter, the tetraethyl orthosilicate of 9.2 mass parts is added.Continue after stirring 20 minutes, by product
Filter out, in being dried under 50 degrees celsius, obtain the silicon oxide vesicle of phosphorylation.By the silica of 100 mass parts phosphorylations
Vesica is added to the aqueous solution of the sulfate of 1000 mass parts (wherein：Titanyl sulfate mass percent concentration is 13.0%；Sulfuric acid
Manganese mass percent concentration is 1.2%；After aluminum sulfate mass percent concentration is stirring in 1.8%) 20 minutes, filter out and taken the photograph in 50
Dried under the conditions of family name's degree, obtain building component S.Titanium elements content is：2.0%；Manganese element content is：0.4%；Aluminium element content
For：0.4%.
Step 2：The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 20000) of 1.0 mass parts, 2.0 mass parts
Polyacrylic acid, the Sodium Polyacrylate of 1.0 mass parts, the polyvinyl alcohol of 1.0 mass parts, the polyvinylpyrrolidine of 5.0 mass parts
Ketone, the ammonium stearate of 0.1 mass parts, 0.5 mass parts building component S is compounded, and is mixed by homogenizer.Reaction
Condition is：Agitating paddle linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder end-product.Sample
It is designated as 19#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 20
1) urea composite denitration agent is prepared：
The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 15000) of 2.0 mass parts, mass parts for 1.0 it is poly-
Acrylic acid, the calcium stearate of 0.1 mass parts is compounded, and is mixed by homogenizer.Reaction condition is：Agitating paddle line
Speed is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 20#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 21
1) urea composite denitration agent is prepared：
The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 15000) of 7.0 mass parts, mass parts for 1.0 it is poly-
Acrylic acid, mass parts are 0.5 Sodium Polyacrylate, and the magnesium stearate of 0.1 mass parts is mixed by homogenizer.Instead
The condition is answered to be：Agitating paddle linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, obtains powder end-product.Sample
Product are designated as 21#.
2) denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
Embodiment 22
1) urea composite denitration agent is prepared：
The urea of 100.0 mass parts, the polyethylene glycol (molecular weight is 20000) of 1.0 mass parts, poly- the third of 2.0 mass parts
Olefin(e) acid, the Sodium Polyacrylate of 1.0 mass parts, the polyvinyl alcohol of 1.0 mass parts, the polyvinylpyrrolidone of 5.0 mass parts, 0.1
The ammonium stearate of mass parts, is mixed by homogenizer.Reaction condition is：Agitating paddle linear velocity is 40 meter per second~80
Meter per second, mixing time is 5~10 minutes, obtains powder end-product.Sample is designated as 22#.
Denitrification test condition be the same as Example 1, denitration the results are shown in Table 1.
(percentage is under the conditions of 750 DEG C, 950 DEG C, 1050 DEG C to the denitrfying agent denitration performance of 1. embodiment of table 1~30 in table
Denitration rate)
Above-mentioned experiment shows, compared to embodiment 20-22, and embodiment 1~19 is respectively provided with higher under low temperature and hot conditions
Denitration rate.
Claims (8)
1. a kind of Modified Urea denitrfying agent, it is characterised in that：
Described Modified Urea denitrfying agent includes urea, high molecular component, modified component and building component, described urea,
The mass ratio of high molecular component, modified component and building component is 100：(0.5~10)：(0.1~10.0)：(0.001~
0.5)；
High molecular component is the additive at least containing more than one following compositions：Polyethylene glycol, polyacrylic acid, polyacrylic acid
Sodium, polyvinyl alcohol, polyvinylpyrrolidone；Modified component is at least containing a kind of following additive of composition：It is ammonium stearate, hard
Fatty acid magnesium, calcium stearate, precipitated calcium carbonate, magnesia, zeolite；Building component is the silica for being loaded with metal sulfate
Vesica.
2. a kind of Modified Urea denitrfying agent as claimed in claim 1, it is characterised in that described metal sulfate, therein
Metallic element is titanium or titanium and one kind at least following element：Manganese, zinc, aluminium.
3. a kind of Modified Urea denitrfying agent as claimed in claim 1, it is characterised in that described silicon oxide vesicle preparation side
Method is as follows：
The preparation of vesica：Under the conditions of at room temperature, by the cocoyl Sodium Glycinate of 0.8~1.5 mass parts and 0.5~1.0 part
Lauryl sodium sulfate is dissolved in the water of 100.0 mass parts, and the mass percent concentration for adding 1.0~1.9 mass parts is 1-
20.0% phosphate aqueous solution, stirs, hereafter, adds the silicon source that mass parts are 8.0~12.0, continues to stir, by product
Filter out, in 25-50 DEG C of drying, obtain the silicon oxide vesicle of phosphorylation.
4. a kind of Modified Urea denitrfying agent as claimed in claim 3, it is characterised in that described silicon source is tetraethyl orthosilicate,
One or more kinds of mixtures in Ludox, sodium metasilicate.
5. a kind of Modified Urea denitrfying agent as claimed in claim 1, it is characterised in that the preparation method of described building component
It is as follows：The mass parts of silicon oxide vesicle 100 of the phosphorylation prepared in claim 3 are added to the quality that mass parts are 1000
Percent concentration is stirs in the aqueous solution of 1-15.0% metal salt after, dried under the conditions of 25-50 DEG C, obtain synergy
Component.
6. a kind of Modified Urea denitrfying agent as claimed in claim 5, it is characterised in that described metal salt solution is：Sulfuric acid
One or more kinds of mixtures in oxygen titanium, zinc sulfate, manganese sulfate, aluminum sulfate.
7. a kind of Modified Urea denitrfying agent described in claim 1, it is characterised in that its preparation method is：It is by mass ratio
100：(0.5~10)：(0.1~10.0)：Urea, high molecular component, modified component and the building component of (0.001~0.5) enter
Row compounding, while stirred, wherein agitating paddle linear velocity is the meter per second of 40 meter per seconds~80, and mixing time is 5~10 minutes, is obtained
To powder end-product.
8. a kind of Modified Urea denitrfying agent as described in claim 1-7 any claims, it is characterised in that described denitration
Agent is used for denitrating flue gas, and out of stock temperature is 750~1050 DEG C.
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| CN114146721A (en) * | 2021-12-01 | 2022-03-08 | 通化鑫鸿新材料有限公司 | Composite denitration agent with biomass carbon powder as carrier and preparation method and application thereof |
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| CN114452813A (en) * | 2021-12-28 | 2022-05-10 | 深圳华明环保科技有限公司 | Production process of solid-state denitration agent |
| CN114452807A (en) * | 2021-12-29 | 2022-05-10 | 深圳华明环保科技有限公司 | Dry-process denitration agent and preparation method thereof |
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Denomination of invention: A modified urea denitrification agent and its preparation method Effective date of registration: 20230907 Granted publication date: 20200630 Pledgee: Shenzhen small and medium sized small loan Co.,Ltd. Pledgor: SHENZHEN HUAMING ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2023980055596 |
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