CN107721365A - The manufacture method of foaming thermal-insulating based on carbide slag desulphurization denitration - Google Patents
The manufacture method of foaming thermal-insulating based on carbide slag desulphurization denitration Download PDFInfo
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- CN107721365A CN107721365A CN201711063702.4A CN201711063702A CN107721365A CN 107721365 A CN107721365 A CN 107721365A CN 201711063702 A CN201711063702 A CN 201711063702A CN 107721365 A CN107721365 A CN 107721365A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/30—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing magnesium cements or similar cements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/062—Purification products of smoke, fume or exhaust-gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a kind of manufacture method of the foaming thermal-insulating based on carbide slag desulphurization denitration.To be respectively that the desulfurizing agent that forms of more than 200 mesh carbide slag, red mud and magnesia adds alkaline industrial waste water and prepares desulfurizer slurry by granularity；Make desulfurizer slurry and 1~15wt% ozone and smoke contacts；Slurries are discharged when absorbing the pH value of slurries to 5.3~6.8, magnesia is added into the slurries of discharge, obtains desulphurization denitration slurries；Raw material comprising desulphurization denitration slurries, magnesia, industrial solid wastes, foaming agent and vinal is mixed, then foaming obtains preform；The preform is conserved 3~8 hours under conditions of temperature is 20~60 DEG C and humidity is 50~100%.The method of the present invention can solve the atmosphere polluting problem that sulfur dioxide and nitrogen oxides are brought, and industrial wastewater, industrial solid wastes can also be utilized to obtain qualified foaming thermal-insulating.
Description
Technical field
The present invention relates to a kind of manufacture method of foaming thermal-insulating, and in particular to one kind is based on mixed base desulfurization denitrification agent
The method of the production foaming thermal-insulating such as desulphurization denitration slurries and other wastes for being formed with ozone.
Background technology
Foam cement product is a kind of inorganic heat insulation material of function admirable.Sulphate aluminium cement is because of the original of its quick setting early strength
Because being widely used in foam cement product.CN104261864A, CN102964097A and CN102863194A etc. are successively open
Development and improvement of the cement insulation board in fire prevention, insulation, energy-conserving and environment-protective, anti-aging, crushing resistance etc. so that foaming
The application of warming plate has obtained significant progress.But in the production process of cement board, the application of ordinary cement
Some problems also be present, moreover, cement belongs to highly energy-consuming construction material, in its production process, disappear along with the substantial amounts of energy
Consumption and serious environmental pollution.Therefore, its future development space is determined to the substitution studies of foam cement product raw material.
At present, artificial aggregate has become one of Main way of building material industry research.Artificial aggregate is mainly with Industry Waste
Slag and urban building waste are that raw material is produced and manufactured.CN1883766A and CN1899670A describes using red mud respectively
Absorb SO in flue gas2Process.Packed absorber is used in this two pieces patent.Although the contact area of packed tower compared with
Greatly, but because pressure drop in the process of running is larger, power consumption is added, and easily there is the problems such as fouling, block in packed tower,
System shutdown even can be caused.CN1654400A discloses a kind of method that high purity gypsum is produced using waste carbide slag, but
It is due to that accessory substance can not effectively remove and cause accessory substance not utilize effectively in flue gas subtractive process.
CN101898083A and CN104437023A discloses the method for carbide slag production desulfurizing agent, the work shape of desulfurizing agent
State require temperature compared with it is high, desulfurizing agent diffusion area is small, adsorption capacity is relatively low, can also increase the dosage of desulfurizing agent, thus cause into
This rising.
In summary, in filed of flue gas purification using solids waste material not effectively improve flue gas in the prior art net
Change efficiency, reduce operating cost, while utilize the technique for purifying accessory substance and industrial solid wastes manufacture construction material.
The content of the invention
It is an object of the invention to provide a kind of manufacture method of the foaming thermal-insulating based on carbide slag desulphurization denitration.This
The one side of invention, by the combination of the technologies such as the desulfurizing agent being made up of carbide slag, magnesia and red mud and oxidizing and denitrating ozone,
The simultaneous removing nitrogen oxides in flue gas desulfurization course, desulphurization denitration collaboration are efficiently carried out.This method has desulphurization denitration dosage
Small, the characteristics of cost is low, denitrification efficiency is high, stable.On the other hand, using desulphurization denitration slurries and combine waste water,
Solid waste produces foaming thermal-insulating, has higher economic value, and further realizes the recycling of waste resource, drops
Low environment pollutes, and mitigates enterprise operation burden.Specifically, the present invention includes herein below.
A kind of manufacture method of the foaming thermal-insulating based on carbide slag desulphurization denitration, comprises the following steps：
(1) pulping stage：It will be aoxidized by 20~55 parts by weight carbide slags, 20~50 parts by weight red muds and 20~45 parts by weight
The desulfurizing agent of magnesium composition adds the industrial wastewater that pH value is 7~12 and prepares desulfurizer slurry；The grain of carbide slag, red mud and magnesia
Degree is more than 200 mesh；
(2) desulphurization denitration step：Make the desulfurizer slurry, ozone and smoke contacts, to form absorption slurries；Ozone
Concentration is 1~15wt%；
(3) plasma discharge step：Slurries are discharged when the pH value of the absorption slurries is to 5.3~6.8, are added into the slurries of discharge
Enter magnesia, obtain desulphurization denitration slurries；
(4) mixed foaming step：Will include 100~200 parts by weight desulphurization denitration slurries, 20~60 parts by weight magnesia,
80~150 parts by weight industrial solid wastes, 10~20 parts by weight of blowing agent, 1~5 parts by weight adjustable solidification agent and 1~15 parts by weight are gathered
The raw material of alcohol fibers mixes, then foaming, so as to obtain preform；
(5) curing step：By the preform under conditions of temperature is 20~60 DEG C and humidity is 50~100%
Maintenance 3~8 hours.
Method in accordance with the invention it is preferred that the weight ratio of the desulfurizing agent and the industrial wastewater is 1:6~10.
Method in accordance with the invention it is preferred that the content of the sulfur dioxide in flue gas is 300mg/Nm3With up to
1000mg/Nm3Hereinafter, and the content of nitrogen oxides is 200mg/Nm3With up to 500mg/Nm3Below.
Method in accordance with the invention it is preferred that the ozone is 50 DEG C~70 DEG C with the temperature during smoke reaction.
Method in accordance with the invention it is preferred that the content of calcium hydroxide is more than 80wt% in the carbide slag, it is described red
The content of calcium oxide and sodium oxide molybdena is more than 40wt% in mud, and in the magnesia activated magnesia content for 60% with
On.
Method in accordance with the invention it is preferred that the magnesia is selected from magnesite light burnt powder, dolomite light burnt powder and analysis
At least one of pure zirconia magnesium, and the content of magnesia is respectively in the magnesite light burnt powder and the dolomite light burnt powder
65wt%~85wt%.
Method in accordance with the invention it is preferred that the industrial solid wastes are selected from clinker, slag, steel slag and iron slag, fine coal
One or more in ash, land plaster, dolomite dust, shale powder.
Method in accordance with the invention it is preferred that one kind in calcium carbide, ammonium carbonate and hydrogen peroxide of the foaming agent or
It is a variety of.
Method in accordance with the invention it is preferred that the adjustable solidification agent in desulfurated plaster, ardealite and the natural gypsum one
Kind is a variety of.
Method in accordance with the invention it is preferred that in mixed foaming step, the stir speed (S.S.) that is blended in is 600 rev/min
For clock with up to less than 1200 revs/min progress, the mixing time added after foaming agent is 4~10s.
The method of the present invention manufactures foaming thermal-insulating using industrial wastewater, solid waste, can effectively solve to pass
Unite foaming insulation board production process in using cement as primary raw material and caused by high energy consumption, the wasting of resources the problem of, make Industry Waste
Slag, grey the like waste all obtain cycling and reutilization.The method of the present invention had not only saved foaming thermal-insulating investment but also substantially reduced
Desulphurization denitration operating cost.In addition, substantial amounts of industrial residue can be added by foaming thermal-insulating produced by the invention, and
Main component magnesium sulfate is prepared by the waste liquid after desulfurization, belongs to desulfuration byproduct, cheap, is significantly reduced
Production cost.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
In the present invention, unless otherwise stated, " part " refers to the number based on weight, " % " and " wt% " refers to be based on
The percentage of weight." vol% " refers to the percentage based on volume.
Number range in the present invention, it is thus understood that specifically disclose the scope upper and lower bound and they between
Each median.Median and any other statement value in any statement value or stated ranges or in the scope
Each less scope between median is also included within the disclosure.These small range of upper and lower bounds can be wrapped independently
Include or exclude in the range of.
The thermal conductivity factor of the foaming thermal-insulating of the present invention is usually 0.05~0.20W/ (mK), and thermal resistance is about common mixed
10~20 times of solidifying soil.The dry volume density of the foaming thermal-insulating of the present invention is usually 300~1000kg/m3, preferably 400~
900kg/m3, equivalent to 1/5~1/8 or so of portland cement concrete, building Integral Loading can be mitigated.The foaming of the present invention
The compression strength of insulation material is usually 1.0~10.0MPa, preferably 1.1~5.0MPa.The suction of the foaming thermal-insulating of the present invention
Water-based smaller, usually less than 10%, preferably less than 9%, relatively independent closed air bubbles and good globality make it have
Certain water resistance.
In order to make full use of waste to manufacture the foaming thermal-insulating as construction material, present inventor is at flue gas
Reason and industrial solid wastes are had made intensive studies using two aspects, and find to pass through magnesia, the red mud from specific proportioning
Cooperative effect can be produced when handling flue gas with ozone with the desulfurizing agent of carbide slag composition, so as to be taken off with higher efficiency desulfurization
Nitre, and obtained desulphurization denitration slurries can also be combined with other industrial solid wastes, manufacture high-quality foaming thermal-insulating.Tool
Body, manufacture method of the invention includes pulping stage, desulphurization denitration step, plasma discharge step, mixed foaming step and maintenance step
Suddenly.Introduce in detail below.
Pulping stage：
To be respectively that the desulfurizing agent that forms of more than 200 mesh carbide slag, red mud and magnesia adds industrial wastewater by granularity
Prepare desulfurizer slurry.The granularity of the present invention is bigger, represents that the particle diameter of particle is smaller.The dosage of carbide slag is 20~55 weight
Part, preferably 25~50 parts by weight；The dosage of magnesia is 20~45 parts by weight, preferably 25~45 parts by weight；The dosage of red mud is
20~50 parts by weight, preferably 25~50 parts by weight.The pH value of industrial wastewater is preferably 7~12, and more preferably 7~10.Desulfurizing agent and
The weight of industrial wastewater is than usually 1:5~10, preferably 1:9.
The carbide slag of the present invention is the discarded object discharged during acetylene production.Preferably, carbide slag of the invention is aqueous
Amount is down to 30~40wt%, in powdery.Inventor has found carbide slag in the desulfurizing agent that is made up of carbide slag, red mud and magnesia
The active calcium ion content is higher, and better than the active calcium ion content in independent carbide slag or common lime stone.In addition, carbide slag in desulfurizing agent
Calcium hydroxide in activity and specific surface area on than after independent carbide slag or Conventional calcination lime stone hydrolysis caused by hydrogen-oxygen
It is high-quality to change calcium, and confirms that the desulphurizing ability of carbide slag is higher than calcium hydroxide.Preferably, calcium hydroxide in carbide slag of the invention
Content is more than 80wt%.
What the red mud of the present invention was discharged when being alumina producing contains offscum in alkali, and the basicity of red mud liquid is 3000~15000mg/
L.Preferably, the content of calcium oxide and sodium oxide molybdena is more than 40wt% in red mud of the invention, and calcium oxide content is led in the range of this
Cause red mud that there is more useful desulfurized effect.It is further preferred that the content of di-iron trioxide is in the red mud of the present invention
More than 30wt%, the ferric oxide in the range of this can exist in the form of hydrated ferric oxide, and it is to H2S has very strong energy of adsorption
Power.
The present invention magnesia (MgO) selected from magnesite light burnt powder, dolomite light burnt powder, analysis pure zirconia magnesium at least
It is a kind of.The content of magnesia is 65%-85% in preferable magnesite light burnt powder and the dolomite light burnt powder.Preferably, oxygen
Change the activated magnesia for including more than 50wt% in magnesium, more preferably more than 60wt% activated magnesia.
Carbide slag, red mud and magnesia are preferably powdered granule thing in the present invention.It is highly preferred that carbide slag, red mud and oxygen
Change the granularity of magnesium to be more than 200 mesh.In carbide slag of the granularity in the range of this, particle is smaller, and specific surface area is larger, is advantageous to improve
The contact area of ozone, desulfurizing agent etc. and flue gas.Be advantageous to improve simultaneously to sulfur dioxide in flue gas (SO2) and nitrogen oxides
(NOX) adsorption function, further improve desulphurization denitration efficiency.Preferably, above-mentioned raw materials are carried out using Ball Mill System
Ball milling is so that its granularity is more than 200 mesh.
Desulphurization denitration step：
The desulphurization denitration step of the present invention includes making the desulfurizer slurry and ozone and smoke contacts.When the flue gas with
When desulfurizer slurry contacts, the sulfur dioxide in magnesium hydroxide, calcium hydroxide and flue gas in desulfurizer slurry reacts to form Asia
Sulfate, sulfate.When contact start, the content of sulfur dioxide in flue gas is 3000mg/Nm3Hereinafter, preferably 1000mg/Nm3
Hereinafter, such as 900mg/Nm3Below.On the other hand, preferably 500mg/Nm3More than, such as 700mg/Nm3More than.Sulfur dioxide
Content it is too low, then the content of the magnesium sulfate generated in desulfurization slurry deficiency, influence the performance of the light concrete product of manufacture.
In the manufacture method of the present invention, when contact start, oxygen content is 10~20vol% in flue gas.This scope
Interior oxygen content is advantageous to sulphite, and further reaction is oxidized to sulfate.Oxygen content is too low, the desulfurization slurry Central Asia manufactured
Sulfate is too high, and the performance for being unfavorable for foaming thermal-insulating improves.In certain embodiments, in order to improve containing for oxygen in flue gas
Amount, can use oxygenation means.For example, air or oxygen is blasted into flue gas.
It should be noted that above-mentioned content of sulfur dioxide and the scope of oxygen content refer to when flue gas is starched with desulfurizing agent first
Content when liquid contacts, can further be reduced with the above-mentioned content of carry out of reaction.
In the manufacture method of the present invention, nitrogen oxides in effluent content is 500mg/Nm3Hereinafter, preferably 100mg/Nm3With
On.The scope of above-mentioned amount of nitrogen oxides refers to when flue gas is first with content during ozone contact, above-mentioned with the carry out of reaction
Content can be reduced further.Preferably, ozone and temperature during smoke contacts are 50~70 DEG C, preferably 50~65 DEG C.It is warm herein
Be advantageous to ozone and NO in the range of degreeXReaction, so as to be advantageous to improve denitration efficiency.Preferably, when first with smoke contacts
When ozone concentration in 1~15wt%, preferably in the range of 5~10wt%.From the aspect of economy and denitration efficiency, more preferably
Ozone concentration is 10wt%.Ozone concentration herein refers to the concentration of the ozone as caused by ozone generator.
It should be noted that the flue gas of the present invention may be from one kind or more in coal-burning boiler, sintering machine, pelletizing and kiln
Kind, the one or more being preferred from sintering machine, pelletizing and kiln.As long as sulfur dioxide in flue gas content, oxygen content and nitrogen
Oxide in above-mentioned prescribed limit, then it is not specific limit flue gas source.The flue gas of the present invention and specified raw material and specific use
The foaming thermal-insulating that the combination of amount scope obtains manufacture meets required performance requirement.
Although being illustrated it should also be noted that, desulfurization and denitration are divided into single two steps herein,
Actually desulfurization can be carried out simultaneously with denitration.When carrying out simultaneously, denitrification efficiency is higher.Inventor speculates that reason may be
NO is NOx main component in flue gas, and it is insoluble in water.It is oxidized when ozone and NO react as NO2Or N2O5Deng high price
The nitrogen oxides of state, the nitrogen oxides of these high-valence states is easily absorbed by water or alkaline matter, so as to promote denitrification process.Separately
Outside, above-mentioned oxidizing process also generates oxygen, and it is sulfate that it, which further promotes sulfite oxidation,.Therefore, based on carbide slag
The combination acts synergistically of desulfurizing agent and ozone, promote the progress of desulphurization denitration.
Dust content can be controlled in 30~50mg/Nm in the flue gas of the present invention3Scope.Dust content in the range of this has
Reaction beneficial to ozone and NOx is carried out.Dust content is too high, and denitration efficiency reduces, and possible cause is the dust of too high amount
Part ozone may have been adsorbed.
Any means known in the art can be used to produce for the ozone of the present invention.For example, occurred by using ozone
Device produces.In addition, ozone can by any device, such as high pressure nozzle supply with smoke contacts.The pressure of high pressure nozzle
Range preferably from 0.8~0.9Mpa.
Plasma discharge step：
The slurries obtained after above-mentioned desulfurization and denitrification step are absorption slurries.With the progress of desulphurization denitration, absorb
The pH of slurries is reduced.Slurries are discharged when the pH value for absorbing slurries is down to 5.3~6.8, preferably 5.5~6.0, obtain desulphurization denitration
Slurries.The content of pH value control magnesium sulfate in the scope, one side absorption slurry is higher, be advantageous to the performance of resulting product
Improve.On the other hand the desulfurizer slurry more renewed by plasma discharge is advantageous to keep high desulfuration efficiency.In order to ensure discharge
For the content of sulfate, it is necessary to add magnesia into the slurries of discharge, its addition is usually 1~20 parts by weight, excellent in slurries
5~15 parts by weight are selected, based on 100 parts by weight slurries.The magnesium sulfate concentration of desulphurization denitration slurries can be 10~20wt%.Herein
In the range of magnesium sulfate concentration, be advantageous to production foaming thermal-insulating intensity improve.The too high or too low ratio of mud is unfavorable
In the raising of performance of heat protective material.
Mixed foaming step：
The mixed foaming step of the present invention includes that 100~200 parts by weight desulphurization denitration slurries, 20~60 parts by weight will be included
Magnesia, 80~150 parts by weight industrial solid wastes, 10~20 parts by weight of blowing agent, 1~5 parts by weight adjustable solidification agent and 1~15 weight
The raw material mixing of part vinal is measured, then foaming, obtains preform.The mixed foaming step of the present invention can adopt
With any mixed media known in the art or mode, as long as can be well mixed and foaming.
Mixing can stir speed (S.S.) be 600 revs/min with up to less than 1200 revs/min, preferably 700~1000 turns/
Carried out under conditions of minute.After foaming agent is added, mixing time is preferably controlled in 4~10s.So be advantageous to improve foaming
The performance of insulation material.
The industrial solid wastes of the present invention are preferably the one or more in clinker, slag, steel slag and iron slag and useless ash.It is excellent
Selection of land, industrial solid wastes of the invention may be selected from clinker and/or slag.In certain embodiments, useless ash choosing of the invention
One or more from flyash, land plaster, dolomite dust and shale powder, preferably flyash.
The industrial solid wastes of the present invention are particle, it is preferable that control the granularity of industrial solid wastes more than 200 mesh.
Because the slag charge granularity of separate sources is larger and granularity heterogeneity is, it is necessary to carry out powdered and homogenization.It is therefore preferred that this
The process for being ground industrial solid wastes such as slag charge can also be included before the mixing of invention, to ensure granularity 200
It is more than mesh.
The foaming agent of the present invention is the material for making object pore-forming.The example includes but is not limited to calcium carbide, ammonium carbonate and double
One or more in oxygen water (hydrogen peroxide).Preferably hydrogen peroxide.The dosage of foaming agent is usually 10~20 parts by weight.It is preferred that
For 10~18 parts by weight.
One kind or more that the example of the adjustable solidification agent of the present invention includes but is not limited in desulfurated plaster, ardealite and the natural gypsum
Kind.The dosage of adjustable solidification agent is usually 1~5 parts by weight, preferably 2~4 parts by weight.The dosage of the vinal of the present invention can be with
For 1~15 parts by weight, preferably 3~10 parts by weight.
In the present invention, preferably magnesia, industrial solid wastes and adjustable solidification agent etc. are first mixed with desulphurization denitration slurries, then
Add foaming agent.In an exemplary embodiment, stir speed (S.S.) not preferably less than 600r/min, and 1200r/ should not be higher than during mixing
Min, slurry mixing time need to be 4~10s, preferably 5~8s after adding foaming agent.
Curing step：
The curing step of the present invention includes being 20~60 DEG C, being preferably 30~50 DEG C in temperature by preform, and humidity
For 50~100%, be preferably to conserve 3~10 hours, preferably 3~8 hours under conditions of 60~80%.
In certain embodiments, curing step of the invention includes the foaming insulation board after form removal being placed into maintenance area
3~8h of initial curing is carried out, curing temperature is 20~60 DEG C, and humidity is 50~100%, then carries out natural curing 10~20 days
.Maintain equipment as usually used those in the art.
The present invention can also include other steps, for example, demoulding step and cutting step.Demoulding step includes pending soaked
Mud insulation material completes maintenance flow, can be stripped when possessing early strength.Cutting step is the foaming that will be provided with some strength
It can be cut after the demoulding of cement heat preserving blanks, cut form adjusts cutting blade progress as needed.
Foaming thermal-insulating is poured into a mould in 100 × 100 × 100mm template, the sample is dried/cold
Freeze, and tested according to JG/T266-2001.
Embodiment 1
(1) desulfurizing agent being made up of magnesia, red mud and carbide slag that granularity is respectively 200 mesh is added into waste water (pH is
10 or so) desulfurizer slurry is mixed and made into, is delivered in the recycle slurry liquid pool of desulfurization tower bottom.The weight of desulfurizing agent and waste water ratio is
1:9.Wherein, the component and part of desulfurizing agent is：
Carbide slag (content of calcium hydroxide is 85wt%) 30 parts by weight；
Red mud (content of calcium oxide and sodium oxide molybdena is 50wt%) 35 parts by weight；
Magnesia (content of activated magnesia is 70%) 35 parts by weight.
(2) ozone is made by ozone generator, and spraying pipeline through ozone booster fan, ozone enters desulphurization denitration tower, cigarette
Nitrogen oxides (especially NO) and ozone contact in gas, it is oxidized.Moisture in oxidized nitrogen oxides and desulfurizing agent connects
Touch and fallen into by absorption in lower slurry circulatory pool.Ozone sprays pipeline and is arranged in tower in 60 DEG C of temperature sections.Desulphurization denitration operating mode
Parameter is shown in Table 1.
The desulphurization denitration duty parameter of table 1
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Inlet flue gas amount (operating mode) | m3/h | 750000 |
| 2 | Inlet flue gas amount (mark condition) | Nm3/h | 508064 |
| 3 | Inlet flue gas temperature | ℃ | 130 |
| 4 | SO2Entrance concentration | mg/Nm3 | 800 |
| 5 | NOxEntrance concentration | mg/Nm3 | 400 |
| 6 | Entrance flue dust | mg/Nm3 | 80 |
| 7 | Humidity of flue gas | Wt% | 4.3 |
(3) slurries in recycle slurry liquid pool are expelled to instead by excavationg pump when the pH value of recycle slurry liquid pool reaches 6.0
Groove is answered, and 8 parts by weight magnesia (being based on 100 parts by weight slurries) are added into reactive tank.
(4) following raw material is added in mixing channel to mix with desulphurization denitration slurries, forms foaming thermal-insulating slurry.
The parts by weight of each raw material are as follows：100 parts of desulphurization denitration slurries, 25 parts of magnesia, industrial solid wastes (main component
50wt%SiO2, 25wt%Al2O3, 9wt%CaO) 100 parts, 15 parts of foaming agent (hydrogen peroxide, technical grade, concentration 27.5%), adjust
Solidifying 4 parts of agent (ardealite), 6 parts of vinal.High-speed stirred 5s.The insulation material slurry of formation is poured into the mold and carried out
Foaming, it is to be foamed to form preform completely.
(5) preform is conserved 8 hours in the environment of temperature 60 C, humidity 50%, finally completes the demoulding, cutting and
Packaging.
The desulfurization off sulfide effect of embodiment 1 is shown in Table 2, and the testing result of the performance of the foaming thermal-insulating of embodiment 1 is shown in Table
3。
Embodiment 2
In addition to using formula as below or step, foaming thermal-insulating is produced in the same manner as in Example 1.
The component and part of desulfurizing agent is：
The parts by weight of carbide slag 40；
The parts by weight of red mud 20；
The parts by weight of magnesia 40.
The parts by weight of each raw material in mixed foaming step are as follows：130 parts of desulphurization denitration slurries, 45 parts of magnesia, industry
120 parts of solid waste, 10 parts of foaming agent, 5 parts of adjustable solidification agent, 5 parts of vinal.High-speed stirred 8s.
The desulfurization off sulfide effect of embodiment 2 is shown in Table 2, and the performance test results of the foaming thermal-insulating of embodiment 2 are shown in Table 3.
Embodiment 3
In addition to using formula as below or step, foaming thermal-insulating is produced in the same manner as in Example 1.
The component and part of desulfurizing agent is：
The parts by weight of carbide slag 20；
The parts by weight of red mud 50；
The parts by weight of magnesia 30.
The parts by weight of each raw material in mixed foaming step are as follows：150 parts of desulphurization denitration slurries, 55 parts of magnesia, industry
100 parts of solid waste, 10 parts of foaming agent, 5 parts of adjustable solidification agent, 15 parts of vinal.High-speed stirred 10s.
The desulfurization off sulfide effect of embodiment 3 is shown in Table 2, and the performance test results of the foaming thermal-insulating of embodiment 3 are shown in Table 3.
The flue gas desulfurization and denitrification effect statistical form of 2 each embodiment of table
| Gas Parameters | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Exiting flue gas amount (operating mode) (Nm3/h) | 628744 | 643379 | 612683 |
| Exhaust gas temperature (DEG C) | 55 | 60 | 60 |
| Sulfur dioxide emissioning concentration (mg/Nm3) | 15 | 10 | 11 |
| Desulfuration efficiency (%) | 98.1 | 98.7 | 98.6 |
| Discharged nitrous oxides concentration (mg/Nm3) | 14 | 10 | 13 |
| Denitration efficiency (%) | 82.0 | 87.1 | 84.0 |
| Export dust concentration (mg/Nm3) | 22 | 25 | 20 |
| Efficiency of dust collection (%) | 94.3 | 93.5 | 95.1 |
| The quantum of output (t/h) of accessory substance | 4.2 | 4.6 | 4.9 |
The performance test results of each embodiment foaming insulation board of table 3
The method desulfuration efficiency of the present invention is up to more than 98%, and denitration efficiency is up to more than 95%.Realize high-efficiency desulfurization and take off
Nitre, while the foaming thermal-insulating produced meets national standard.
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill
Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.
Claims (10)
1. a kind of manufacture method of the foaming thermal-insulating based on carbide slag desulphurization denitration, it is characterised in that comprise the following steps：
(1) pulping stage：Will be by 20~55 parts by weight carbide slags, 20~50 parts by weight red muds and 20~45 parts by weight magnesia groups
Into desulfurizing agent add pH value be 7~12 industrial wastewater prepare desulfurizer slurry；The granularity of carbide slag, red mud and magnesia is equal
More than 200 mesh；
(2) desulphurization denitration step：Make the desulfurizer slurry, ozone and smoke contacts, to form absorption slurries；The concentration of ozone
For 1~15wt%；
(3) plasma discharge step：Slurries are discharged when the pH value of the absorption slurries is to 5.3~6.8, oxygen is added into the slurries of discharge
Change magnesium, obtain desulphurization denitration slurries；
(4) mixed foaming step：Will include 100~200 parts by weight desulphurization denitration slurries, 20~60 parts by weight magnesia, 80~
150 parts by weight industrial solid wastes, 10~20 parts by weight of blowing agent, 1~5 parts by weight adjustable solidification agent and 1~15 weight account polyethylene
The raw material of alcohol fiber mixes, then foaming, so as to obtain preform；
(5) curing step：The preform is conserved 3 under conditions of temperature is 20~60 DEG C and humidity is 50~100%
~8 hours.
2. according to the method for claim 1, it is characterised in that the weight ratio of the desulfurizing agent and the industrial wastewater is 1:
6~10.
3. according to the method for claim 2, it is characterised in that the content of the sulfur dioxide in flue gas is 300mg/Nm3With
Up to 1000mg/Nm3Hereinafter, and the content of nitrogen oxides is 200mg/Nm3With up to 500mg/Nm3Below.
4. according to the method for claim 3, it is characterised in that the ozone is 50 DEG C with the temperature during smoke reaction
~70 DEG C.
5. according to the method for claim 1, it is characterised in that in the carbide slag content of calcium hydroxide be 80wt% with
On, the content of calcium oxide and sodium oxide molybdena is more than 40wt% in the red mud, and in the magnesia activated magnesia content
For more than 60%.
6. according to the method for claim 5, it is characterised in that it is light that the magnesia is selected from magnesite light burnt powder, dolomite
Burn at least one of powder and analysis pure zirconia magnesium, and magnesia in the magnesite light burnt powder and the dolomite light burnt powder
Content is respectively 65wt%~85wt%.
7. according to the method for claim 6, it is characterised in that the industrial solid wastes be selected from clinker, slag, slag,
One or more in scum, flyash, land plaster, dolomite dust, shale powder.
8. according to the method for claim 7, it is characterised in that the foaming agent is selected from calcium carbide, ammonium carbonate and hydrogen peroxide
In one or more.
9. according to the method for claim 8, it is characterised in that the adjustable solidification agent is selected from desulfurated plaster, ardealite and natural
One or more in gypsum.
10. according to the method for claim 9, it is characterised in that described to be blended in stir speed (S.S.) in mixed foaming step
For 600 revs/min with up to less than 1200 revs/min progress, the mixing time added after foaming agent is 4~10s.
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| CN106467387A (en) * | 2015-08-19 | 2017-03-01 | 北京中晶环境科技股份有限公司 | A kind of magnesium processes desulfurization produces the device and method of magnesium sulfate foamed bricks |
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| CN102942381A (en) * | 2012-11-08 | 2013-02-27 | 沈阳建筑大学 | Light building material prepared by using iron tailing and preparation method of light building material |
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