CN108373315A - A kind of device and method of magnesium processes desulfurization production magnesium sulfate foamed bricks - Google Patents
A kind of device and method of magnesium processes desulfurization production magnesium sulfate foamed bricks Download PDFInfo
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- CN108373315A CN108373315A CN201810414904.7A CN201810414904A CN108373315A CN 108373315 A CN108373315 A CN 108373315A CN 201810414904 A CN201810414904 A CN 201810414904A CN 108373315 A CN108373315 A CN 108373315A
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- flue gas
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- gas desulfurization
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Abstract
The present invention provides a kind of foaming product and process units and method, described device includes：Flue gas desulfurization device, slurry storage device, consersion unit, magnesia supply arrangement, sulfuric acid supply arrangement, useless grey supply arrangement, slag charge supply arrangement, foaming component supply arrangement, other additive supply arrangements and hybrid process equipment.Wherein, the slurry storage device, consersion unit, magnesia supply arrangement, sulfuric acid supply arrangement, useless grey supply arrangement, slag charge supply arrangement, foaming component supply arrangement, other additive supply arrangements and hybrid process equipment are respectively positioned on the outside of the flue gas desulfurization device.The present invention can be completed at the same time magnesium oxide method flue gas desulfurization technique and magnesium sulfate foaming product production technology, and low cost, the excellent foaming product of physical and chemical performance is made.
Description
It is " on August 19th, 2015 " that the application, which is application No. is " 201510512552.5 ", the applying date, entitled
A kind of divisional application of the patent application of " device and method of magnesium processes desulfurization production magnesium sulfate foamed bricks ".
Technical field
The present invention relates to a kind of foaming product and process units and method more particularly to a kind of magnesium sulfate foaming product and lifes
Produce device and method, the more particularly to device of a kind of magnesium oxide method flue gas desulfurization course synchronous production magnesium sulfate foamed bricks and side
Method.The device of the invention and its method belong to green, energy-saving and environmental protection type foaming product process units and technique, are particularly suitable for
Coal-burning boiler, sintering machine, pelletizing, rotary kiln etc. need the field of flue gas desulfurization.
Background technology
General magnesium sulfate cement is not the hydraulic cement such as Portland cement etc, can be degenerated when impregnating in water.
General special cement, in magnesium oxysulfide concrete or magnesia oxychloride cement or Sorel (Sorel) cement production process, magnesium sulfate is usual
It is used as auxiliary material.For example, patent document CN1156701A disclose magnesium sulfate can be as the swelling agent of cement, incorporation
It is the 0.3~4.0% of cement weight.Previous professional knowledge, document think that in cement formula, the dosage of magnesium sulfate should not mistake
Otherwise height can influence the comprehensive performance of cement and can increase production cost.As patent document CN 102701616A disclose one
Kind High-strength magnesian coal ash clinker-free cement, including：100 parts of flyash；30~40 parts of light calcined magnesia；Epsom salt 10~
15 parts；2~4 parts of calcium sulfate, ferrous sulfate or aluminum sulfate；0.5~1.0 part of phosphoric acid or phosphoric acid；50~100 parts of water.Patent text
It offers and is put back into using flyash as raw materials for production, reduce environmental pollution, but the dosage of magnesium sulfate is much smaller than oxidation
Magnesium, and the compression strength of gained cement needs to be further improved.Patent document CN102924038A discloses a kind of modified sulphur
Oxygen magnesium cement, including 100 parts of magnesia, 0.05~10 part of additive, mass fraction are 10%~30% magnesium sulfate solution 50
~200 parts and 0~300 part of filler；Gained cement have excellent mechanical property and water resistance, compression strength still up for
It further increases, and density is larger.Patent document CN 103396022A disclose a kind of magnesium cement composite powder material and its preparation
Technique, including 100 parts of magnesia and 35~75 parts of magnesium chlorides；Alternatively, 100 parts of magnesia and 35~80 parts of magnesium sulfate.It should
The main component of magnesium cement is configured to semi-finished product powder by patent document, and water is added to can be used；But strictly to control magnesium sulfate
Dosage.
The comprehensive physical performance of magnesium sulfate cement in above patent document is also undesirable, such as cannot have hair simultaneously
Lightweight and the high performance of intensity after bubble.
In addition, the Chinese patent application of Publication No. CN103265263A discloses a kind of preparation side of magnesium oxysulfide concrete
Method mainly uses Waste Sulfuric Acid, magnesia, flyash, phosphoric acid or dihydric phosphate according to certain proportioning, puts into blender and stir
Obtained magnesium oxysulfide concrete after mixing uniformly.The cement includes：100 parts of magnesia, 0~300 part of filler, 0.05~10 part of additive,
10~200 parts of industrial waste sulfuric acid, 0~100 part of water.This method reacts production magnesium sulfate by Waste Sulfuric Acid with magnesia, is reacting
It is influenced in the process by environment temperature, reaction time, crystalline quality etc., is formed by magnesium sulfate quality, quantity presence uncertainty,
To finally influence the quality of cement.There is certain danger, entire production process to be caused to ambient enviroment for Waste Sulfuric Acid transport
Certain influence needs to take stringenter safeguard measure, and therefore, production cost is relatively high, and economy is poor, limits it
It promotes and applies.
On the basis of above-mentioned background technology, the present inventor retrieved a large amount of domestic data, without based on sulfuric acid
The foam process of magnesium cement, and there is the material of certain similitude with magnesium sulfate, such as the foaming technique of magnesia oxychloride cement, in the U.S.
The technology of production foaming magnesium oxychloride cement is disclosed in patent application US 4,041,929.The method use foaming agents "
Norgan Expander ", it is actually a kind of positive lactic acid of the metal of Mg (salt), the scene during magnesia foamed bricks produce
Reaction forms a kind of gas (hydrogen) of danger, which makes mixture foam.US 4,992,481 then disclose polycarboxylic acids and
Its salt (col.6；Lines 15.16) and many other organic polymer materials be used in magnesia foamed bricks production in, but without public affairs
Opening any of these materials causes to foam.European patent application EP 454660 discloses a kind of Sorel foamed bricks of protection, it
With improved water resistance, with MgO, MgCl2Based on the mixture of inorganic filler, it contains water-soluble, polymerization
Or the synthetic resin of polycondensation, the resin include water soluble polycarboxylic acid, which does not mention in magnesia foamed bricks production period yet
Between so that magnesia foamed bricks is carried out any blistering or foaming.German patent application DE 3832-287 are disclosed citric acid and oxalic acid
Water resistance for improving magnesia foamed bricks, but this article does not mention these reagents and makes the possibility that magnesia foamed bricks foam
Property.In fact, as present patent application experiment proves, these reagents do not cause cement foamed substantially.
It can be clearly seen from described above, stand in economy, ease of handling and formed by foaming sulfuric acid magnesium products system
At various density the quality of product and the viewpoint of economy on see, above-mentioned given data can not provide coherent reference.
Invention content
In order to overcome the deficiencies of existing technologies, the present invention provides a kind of foaming product and process units and methods, to reach
To a kind of purpose of physical and chemical performance and the preferable foaming product of economic performance and its process units and method of offer.The present invention is special
The field of flue gas desulfurization is needed suitable for coal-burning boiler, sintering machine, pelletizing, rotary kiln etc., can complete the same of flue gas desulfurization
When produce the foaming product.
The process units of foaming product provided by the invention includes following equipment：
Flue gas desulfurization device for removing the sulfur dioxide in flue gas using magnesium oxide method, and forms flue gas desulfurization glue size,
Contain magnesium sulfate in the flue gas desulfurization glue size；
Slurry storage device, for storing the flue gas desulfurization glue size from flue gas desulfurization device, and by flue gas desulfurization glue size
It is delivered to consersion unit；
Consersion unit, for receiving the flue gas desulfurization glue size from slurry storage device, and by being starched to the flue gas desulfurization
Sulfuric acid and magnesia are added in liquid to improve the magnesium sulfate concentration of the flue gas desulfurization glue size, to form magma, in the magma
Contain magnesium sulfate crystals；
Magnesia supply arrangement, for providing foaming product magnesia；
Sulfuric acid supply arrangement, for providing foaming product sulfuric acid；
Useless ash supply arrangement, for providing foaming product with useless ash；
Slag charge supply arrangement, for providing foaming product slag charge；
Foaming component supply arrangement, for providing foaming component；
Other additive supply arrangements, for providing foaming product other additives, other described additives do not wrap
Containing useless ash, slag charge and foaming component；
Hybrid process equipment comes from for magma, the magnesia from magnesia supply arrangement of autoreaction equipment in future
The useless ash of useless ash supply arrangement, the foaming product slag charge from slag charge supply arrangement, the foaming from additive supply arrangement
Other additives of product and foaming component hybrid process from foaming component supply arrangement, to form foaming product；
Wherein, the slurry storage device, consersion unit, magnesia supply arrangement, sulfuric acid supply arrangement, useless ash supply are set
Standby, slag charge supply arrangement, other additive supply arrangements, foaming component supply arrangement and hybrid process equipment are respectively positioned on the cigarette
The outside of desulfurization equipment.
Device according to the present invention, it is preferable that the top in the flue gas desulfurization device, which is equipped with, absorbs spraying zone,
For removing the sulfur dioxide in flue gas using magnesium oxide method, and form flue gas desulfurization glue size.
Device according to the present invention, it is preferable that described device further includes slag charge milling apparatus, is used for foaming product
It is ground to powder with slag charge, and is delivered to slag charge supply arrangement.
Device according to the present invention, it is preferable that the process units of the foaming product is the dress for producing foamed bricks
It sets.
The present invention also provides the methods for producing foaming product using above-mentioned apparatus, include the following steps：
1) flue gas desulfurization step：The sulfur dioxide in flue gas, and shape are removed using magnesium oxide method in flue gas desulfurization device
At flue gas desulfurization glue size, contain magnesium sulfate in the flue gas desulfurization glue size；
2) step is discharged in slurries：The flue gas desulfurization glue size of flue gas desulfurization device is expelled to slurry storage device；
3) reaction step：The flue gas desulfurization glue size from slurry storage device is received in consersion unit, and to the flue gas
Addition sulfuric acid and magnesia are described to form magma to improve the magnesium sulfate concentration of the flue gas desulfurization glue size in desulfurization slurry
Contain magnesium sulfate crystals in magma；
4) hybrid process step：In hybrid process equipment future autoreaction equipment magma, from magnesia supply set
Standby magnesia, the useless ash from useless grey supply arrangement, the foaming product slag charge from slag charge supply arrangement add from other
Add other additives of foaming product of agent supply arrangement and the foaming component hybrid process from foaming component supply arrangement, with
Form foaming product.
Method according to the present invention, it is preferable that in step 3), the weight ratio of magnesium sulfate and magnesia in the magma
0.8~1.2:1.
Device according to the present invention, it is preferable that in step 4),
The slag charge be selected from clinker, slag, steel slag and iron slag it is one or more；
The useless ash is one or more in flyash, land plaster, dolomite dust, shale powder；
Other described additives include one or more selected from following additive：Stearic acid, calcium stearate, stearic acid
Zinc, silicon rubber, polyester fiber, glass fibre, phosphoric acid, dihydric phosphate, dibasic alkaliine, tartaric acid, tartrate and amino
Trimethylene phosphonic, polypropylene, polyacrylonitrile, lignin, hydroxypropyl methyl cellulose or siloxanes；
The foaming component includes organic foaming agent or inorganic foaming agent；The organic foaming agent be selected from organic carboxyl acid,
The acid anhydrides of organic carboxyl acid or monocarboxylate it is one or more；The inorganic foaming agent is selected from sodium bicarbonate or ammonium carbonate.
Device according to the present invention, it is preferable that the foaming component further includes air entraining agent, and the air entraining agent is selected from
Your oil, dodecyl sodium sulfate, neopelex, oil hydroxyl are spat in the rosin resin of saponification, Wen Shaer resins, saponification
Sulfonated salts in it is one or more.
Foaming product provided by the invention is prepared by foaming raw material.The foaming raw material includes 20~40 parts by weight
Flue gas desulfurization glue size, the magnesia of 20~30 parts by weight, the sulfuric acid of 6~10 parts by weight, the slag charge of 15~30 parts by weight, 20~
The useless ash of 40 parts by weight, other additives of 5~20 parts by weight；
The foaming raw material further includes foaming component, and the foaming component includes foaming agent and air entraining agent, and foaming agent is used
Amount is 3wt%~10wt% of magnesia dosage, and air entraining agent dosage is 3wt%~10wt% of magnesia dosage.
Foaming product according to the present invention, it is preferable that the foaming agent is stearic acid, positive lauric acid/dodecanoic acid or polypropylene
Acid；The air entraining agent is neopelex.
The physical and chemical performance and economic performance of foaming product provided by the invention are preferable, can be incited somebody to action using described device and method
Magnesium oxide method flue gas desulfurization technique and magnesium sulfate foamed bricks production technology perfect adaptation so that the two synchronize carry out and described in producing
Foaming product.The device of the invention and method eliminate homogenizing during traditional cement production, firing, thermally decompose link in advance,
It solves the problems, such as the liquid waste processing that magnesium oxide method desulfurization generates, solves enterprise using the too big nothing of desulfurated plaster amount after calcium method desulfurization
The problem of method digestion process, the process of plate and frame filter press slagging-off is eliminated, slurries are directly used in the production of foaming product, solve
The intractable problem of desulfurization project solid waste.The device of the invention and method are ensureing to solve the normal desulfurization item of enterprise's flue gas
Under part, so that slag, grey the like waste that industrial enterprise's internal pair production generates all is obtained cycling and reutilization, be that one kind both having saved foaming
The investment of production of articles line greatly reduces desulfurization operation cost, had not only ensured enterprise's flue gas desulfurization facilities high-efficiency operation but also makes each again
Class waste is able to the green of cycling and reutilization, energy-saving and environmental protection technology.Foaming product produced by the present invention has high quality, low
The characteristics of density, good physical properties are at low cost, are excellent lightweight aggregate products.
Description of the drawings
Fig. 1 is a kind of schematic diagram of the device of flue gas desulfurization production foaming product of the present invention.
The reference numerals are as follows：1 be flue gas desulfurization device, 2 be absorb spraying zone, 3 be that discharge pump, 4 slurry storages are set
It is standby, 5 be consersion unit, 6 be magnesia supply arrangement, 7 be sulfuric acid supply arrangement, 8 be hybrid process equipment, 9 be slag charge supply
Equipment, 10 for useless grey supply arrangement, 11 are other additive supply arrangements, 12 are foaming component supply arrangement, 13 are that drying is set
It is standby, 14 be packaging facilities.
Specific implementation mode
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously
It is without being limited thereto.
In the present invention, the magnesium oxide method flue gas desulfurization is a kind of wet desulphurization work well known to those skilled in the art
Skill, which is not described herein again its technological principle.The present invention magnesium oxide method flue gas desulfurization as it is well known to those skilled in the art that
Sample, using magnesia as the main ingredient of desulfurizing agent.But the desulfurizing agent of the present invention is not intended to limit the other compositions of addition and (such as aoxidizes
Calcium, quick lime etc.).
" foaming product " of the present invention include through a variety of materials made from the hybrid process equipment, semi-finished product and at
Product, such as can be cement, foamed bricks, light wall material, heat-insulating fireproof material, porous adsorbing material.
Correspondingly, the specific setting of " the hybrid process equipment " can be according to the type of " foaming product " to be obtained
And be arranged, this is well-known to those skilled in the art." hybrid process " means the processing to various supplied materials, can be only mixed
It closes, can also include machine-shaping.
<The process units of flue gas desulfurization foaming product>
The process units of flue gas desulfurization foaming product provided by the invention can be completed at the same time magnesium oxide method flue gas desulfurization work
Skill and magnesium sulfate foaming product production technology, foaming product low cost obtained, physical and chemical performance are excellent.Described device includes：Cigarette
Desulfurization equipment, slurry storage device, consersion unit, magnesia supply arrangement, sulfuric acid supply arrangement, useless grey supply arrangement, slag
Expect supply arrangement, foaming component supply arrangement, other additive supply arrangements and hybrid process equipment.Wherein, the slurries storage
Deposit equipment, consersion unit, magnesia supply arrangement, sulfuric acid supply arrangement, useless grey supply arrangement, slag charge supply arrangement, foaming group
The outside for dividing supply arrangement, other additive supply arrangements and hybrid process equipment to be respectively positioned on the flue gas desulfurization device.Optionally
Ground, described device further include drying equipment and/or packaging facilities.
The flue gas desulfurization device of device of the present invention includes absorbing spraying zone, for being absorbed in flue gas using magnesium oxide method
Sulfur dioxide, form the absorption slurries (i.e. flue gas desulfurization glue size) of containing magnesium sulfate.Also contain part sulfurous in the absorption slurries
Sour magnesium in order to express easily referred to herein as the absorption slurries of containing magnesium sulfate, but does not indicate that and contains only magnesium sulfate, includes to other
Object is not excluded.It is the titanium dioxide absorbed using magnesium hydroxide slurry in flue gas that magnesium oxide method of the present invention, which absorbs,
Sulphur.Those desulfurization used in magnesium oxide method removing flue gas commonly used in the art can be used by absorbing preparation used in spraying zone
Agent slurries.Preferably, desulfurizing agent of the invention can use in CN102745726A, CN102745725A, CN102836636A
Those of disclosed desulfurizing agent.For example, the embodiment 1 of CN102745726A or 2 those disclosed desulfurizing agents.Here, by above-mentioned
The full content of patent application is incorporated herein by reference.By these desulfurizing agents it is evenly dispersed in water i.e. obtain hydrogeneous magnesia
Desulfurizer slurry.According to embodiment of the present invention, in the uptake zone of the flue gas desulfurization device of the present invention, make flue gas
With magnesium hydroxide slurry counter current contacting in uphill process, the sulfur dioxide in flue gas occurs to neutralize anti-with magnesium hydroxide slurry
It answers, forms the absorption slurries of containing magnesium sulfate.In this embodiment, oxidized magnesium absorbs the absorption slurry for being formed by containing magnesium sulfate
Liquid is fallen into the serum recycle area in flue gas desulfurization device.Preferably, in uptake zone of the present invention, setting multistage absorption sprays
Drenching layer, preferably sulfur dioxide absorption.In absorption spraying layer of the present invention, preferably by slurry spraying sprinkler part to
Under eject the magnesium hydroxide slurry of atomization.Atomizing spray component of the present invention is not particularly limited, this can be used
Those of known to field.Preferably, the atomizing spray component of the present invention is corrosion-resistant atomizing spray component, it is more preferably acidproof
Alkali corrosion resistance atomizing spray component.According to embodiment of the present invention, the atomizing spray component preferably includes stainless steel
Nozzle.
The flue gas desulfurization device of the present invention further includes serum recycle area, the suction for receiving the containing magnesium sulfate from uptake zone
Slurries (i.e. flue gas desulfurization glue size) are received, and the absorption slurries part is delivered to uptake zone, another part is delivered to reaction
Equipment.Serum recycle area of the present invention is preferably provided at the bottom of flue gas desulfurization device.An implementation according to the present invention
Mode, the serum recycle area are communicated through circulating pump with uptake zone, for magnesium hydroxide slurry or absorption slurries to be delivered to suction
It receives area and carries out magnesium oxide method absorption, meanwhile, the serum recycle area is communicated through discharge pump with consersion unit, is used for containing magnesium sulfate
Absorption slurries be delivered to consersion unit.Preferably, the serum recycle area through slurries transfer pipeline and is absorbed by circulating pump
The absorption spraying layer of spraying zone communicates.
The slurry storage device of device of the present invention, for receive from flue gas desulfurization device containing magnesium sulfate
Absorb slurries (i.e. flue gas desulfurization glue size).The slurry storage device can be connected to the flue gas desulfurization with pipeline by discharge pump
The serum recycle area of equipment when sulfuric acid content of magnesium reaches a certain range, is arranged the slurries in flue gas desulfurization device by discharge pump
Go out to slurry storage device.The slurry storage device can be groove-like structure, or the container of various other moulding.
The consersion unit of device of the present invention is connected to the slurry storage device, and slurries storage device is come from for increasing
Flue gas desulfurization glue size magnesium sulfate concentration.It is allowed to reaction by the way that sulfuric acid and magnesia are added in slurries and forms magnesium sulfate, carry
The concentration of high magnesium sulfate slurries.The supply of sulfuric acid and magnesia can respectively by being connected to consersion unit sulfuric acid supply arrangement
It is completed with magnesia supply arrangement.
Magnesia supply arrangement of the present invention supplies foaming product magnesia into consersion unit.The magnesia
Magnesia in supply arrangement can be stored and be supplied in the form of magnesia solid powder, can also be with magnesium hydroxide slurry
Form stores and supply.The addition of magnesia is not particularly limited in the present invention, can be according to sulphuric acid and sulfuric acid
The concentration of magnesium is specifically adjusted.The material that magnesia supply arrangement of the present invention is preferably corroded by acid-fast alkali-proof is made,
Its shape and structure are not particularly limited, and design well known in the art can be used.
Sulfuric acid supply arrangement of the present invention supplies foaming product sulfuric acid into consersion unit.The sulfuric acid supply is set
Standby interior sulfuric acid can be production spent acid, can also be the sulfuric acid of purchase.It is preferred that being deposited in the form of certain density sulfuric acid solution
Storage and supply.The addition of sulfuric acid is not particularly limited in the present invention, can be according to the dense of magnesia addition and magnesium sulfate
Degree is specifically adjusted.Sulfuric acid supply arrangement of the present invention preferably by acid-fast alkali-proof corrode material be made, shape and
Structure is not particularly limited, and design well known in the art can be used.
The useless grey supply arrangement of the present invention is for providing useless ash.The supply arrangement be it is known in the art those, here
It repeats no more.
The slag charge supply arrangement of the present invention, for providing foaming product slag charge.Due to separate sources slag charge granularity compared with
Big and granularity is inhomogenous, therefore the device of the flue gas desulfurization production foamed bricks of the present invention can also include carrying out powdered to slag charge
With the slag charge milling apparatus of Homogenization Treatments, for foamed bricks to be ground to powder with slag charge, and it is delivered to slag charge supply arrangement.
The slag charge milling apparatus of the present invention is primarily referred to as the ball mill of field of cement production.The ball milling function grinds slag, slag, powder
The waste residues such as coal ash, industrial refuse, the product after grinding can reach 400m2/ kg~600m2The specific surface area of/kg.
The foaming component supply arrangement of the present invention is used to provide the foaming component used in foaming product.Other additives supply
Equipment, for providing foaming product other additives, referred to as " other additives " be in order to the useless ash, slag charge and foaming
Component is distinguished.The additive supply arrangement and foaming component supply arrangement be all it is known in the art those, here
It repeats no more.
Useless grey supply arrangement, slag charge supply arrangement, foaming component supply arrangement, other additive supply arrangements of the present invention
It is preferably set up in parallel, respectively the base feed into hybrid process equipment.
Slurries, magnesia from magnesia equipment of the hybrid process equipment of the present invention for autoreaction equipment in future,
Useless ash, the foaming product slag charge from slag charge supply arrangement from useless grey supply arrangement, come from foaming component supply arrangement
Foaming component, and come other from other additive hybrid process of additive supply arrangement to form foaming product.It is described mixed
Closing the specific setting of process equipment can be arranged according to the type for the foaming product to be obtained.Foaming system of the present invention
Product include a variety of materials, finished product and semi-finished product made from the mixing material, such as can be cement, foamed bricks, light weight wall
Body material, heat-insulating fireproof material, porous adsorbing material.The foaming product can be processed directly or secondary operation is building structure
Part, including as construction material, engineering packing material (such as girt strip), fire-resistant door core filler, fire proofing, interior heat insulating material for external,
Sound insulation and heat-insulated composite material etc..Those skilled in the art can select known mixing to add according to the type of foaming product
Construction equipment.Therefore, the hybrid process equipment can only have the construction for realizing mixed function, it is possible to have add to realize
Work is molded the construction of function.When only for realizing mixed function, mixing apparatus of the invention can be mixed for uniaxial mixing machine, twin shaft
Conjunction machine or blender, preferably blender.
Device of the present invention can also include drying equipment, foaming product to be dried.Due to the present invention
Foaming product form of diverse, certain products can not by drying equipment naturally dry, so drying equipment is optional to set
It is standby.Selected drying equipment those of can be well known to those skilled in the art, such as can be configuration hot air apparatus
Vibrating fluid bed dryer.
The device of the flue gas desulfurization production foamed bricks of the present invention can also include packaging facilities, such as hair well known in the art
Brewage packaging facilities can also use cement packing equipment.Which is not described herein again.
Optionally, device of the present invention further includes defogging equipment, for carrying out dehydrating demisting to desulfurization fume.This hair
Its type of defogging equipment and process conditions are not particularly limited used in bright, can be used defogging equipment well known in the art and
Technique.According to embodiment of the present invention, in defogging equipment self-absorption in future spraying zone desulfurization fume dehydrating demisting
It is discharged afterwards from the exhanst gas outlet of flue gas desulfurization device.
<The method for producing foaming product>
The present invention is completed at the same time magnesium oxide method flue gas desulfurization technique and sulphur using the method for above-mentioned apparatus production foaming product
The excellent foaming product of low cost, physical and chemical performance is made in sour magnesium foaming product production technology.This method includes：Flue gas desulfurization walks
Suddenly, slurries discharge step, reaction step and hybrid process step.Optionally, the method further includes that drying steps and packaging walk
Suddenly.
The flue gas of the flue gas desulfurization step can be the flue gas from coal-burning boiler, sintering machine, pelletizing or kiln；It is preferred that
For the flue gas from coal-burning boiler, sintering machine or kiln；The more preferably flue gas from coal-burning boiler or sintering machine.Due to above-mentioned
There are a certain amount of oxygen and content of sulfur dioxide are moderate in flue gas, the purity of magnesium sulfate product can be improved.According to this hair
A bright specific implementation mode, the content of sulfur dioxide in the flue gas can be 300mg/Nm3~40000mg/Nm3, excellent
It is selected as 500mg/Nm3~30000mg/Nm3, more preferably 1000mg/Nm3~5000mg/Nm3.In flue gas of the present invention
Oxygen content can be 3~18vt%, preferably 9~18vt%, more preferably 12~18vt%.
The flue gas desulfurization step of the present invention is to remove the titanium dioxide in flue gas using magnesium oxide method in flue gas desulfurization device
Sulphur, and flue gas desulfurization glue size is formed, contain magnesium sulfate in the flue gas desulfurization glue size.In the specific embodiment party of the present invention
In case, the top in the flue gas desulfurization device, which is equipped with, absorbs spraying zone, and flue gas enters from the lower part of flue gas desulfurization device to be set
Standby internal, by absorbing spraying zone in uphill process, the sulfur dioxide in flue gas is absorbed, and purified flue gas is de- from flue gas
The top of sulphur equipment is discharged.Preparation used in spraying zone is absorbed as previously mentioned, which is not described herein again.
The slurries discharge step of the present invention is the pH when recycle slurry liquid pool in flue gas desulfurization device, density, sulfuric acid content of magnesium
When reaching a certain range, the flue gas desulfurization glue size in recycle slurry liquid pool is expelled to by slurry storage device by discharge pump.It is preferred that
Ground, when the pH value of flue gas desulfurization glue size is 4.5~6.5, serum density is 1000~1150kg/m3, sulfuric acid content of magnesium reaches
When 30wt% or more, the flue gas desulfurization glue size in recycle slurry liquid pool is expelled to slurry storage device.
The present invention reaction step be：The flue gas desulfurization glue size from slurry storage device is received in consersion unit, and
Sulfuric acid and magnesia are added into the flue gas desulfurization glue size to improve the magnesium sulfate concentration of the flue gas desulfurization glue size, to form crystalline substance
It starches, contains magnesium sulfate crystals in the magma.Added magnesia is preferably excessive, the weight of magnesium sulfate and magnesia after reaction
Than that can be between 0.8~1.2.
The hybrid process step of the present invention is the magma of autoreaction equipment in future, the oxidation from magnesia supply arrangement
Magnesium, the useless ash from useless grey supply arrangement, the foaming product slag charge from slag charge supply arrangement are supplied from other additives
Other additives of the foaming product of equipment and foaming component hybrid process from foaming component supply arrangement, to form foaming
Product.
The slag charge can be selected from clinker, slag, steel slag and iron slag it is one or more.Preferably, slag charge of the invention is
Clinker and/or slag.In process of production, power plant, steel mill, the various slag class such as stoves that generation is produced in chemical plant can be collected
It is spare to be sent into slag library when being then ground into the powdery for needing specification via slag charge milling apparatus for slag, slag, steel slag and iron slag.
The useless ash of the present invention can be to be one or more in flyash, land plaster, dolomite dust, shale powder, preferably
Flyash.Ash (such as fine coal of deduster lower part discharge after the equipment such as power plant, steel mill's coal-burning boiler, sintering machine, shaft furnace, pelletizing
Ash) it is all spare in the useless grey library of income.
The foaming component of the present invention includes organic foaming agent or inorganic foaming agent；The organic foaming agent, which is selected from, to be had
Machine carboxylic acid, the acid anhydrides of organic carboxyl acid or monocarboxylate it is one or more；The inorganic foaming agent is selected from sodium bicarbonate or carbon
Sour ammonium.Preferably, the foaming component further includes air entraining agent, and the air entraining agent is selected from the rosin resin of saponification, Wen Shaer trees
Fat, saponification one or more of the sulfonated salts for spitting your oil, dodecyl sodium sulfate, neopelex, oil hydroxyl
Combination.
Other additives of the present invention include one or more selected from following additive：Stearic acid, calcium stearate, tristearin
Sour zinc, silicon rubber, polyester fiber, glass fibre, phosphoric acid, dihydric phosphate, dibasic alkaliine, tartaric acid, tartrate and ammonia
Base trimethylene phosphonic, polypropylene, polyacrylonitrile, lignin, hydroxypropyl methyl cellulose or siloxanes.
The present inventor during the experiment, surprisingly it has been found that when by a certain amount of foaming component and MgO, MgSO4, slag
Material, useless ash, other above-mentioned additives and water can form density and substantially reduce and the general cement of intensity ratio much higher more when mixing
Porous materials can change the density of product to form different performance, different unit mass by adjusting the amount of the above components
The product of (unit weight).This cement made that is formulated also has very strong water resistance, lower temperature resistance.It is used to form foaming product
Specific carboxylic acid, acid anhydrides and its carboxylate (such as Na+, Mg2+, Ca2+, A13+, etc.) also can with cannot cause product foam it is other
Carboxylic acid, their acid anhydrides and their carboxylate are used in combination with.This combination can form with improved water resistance, change
The foaming magnesium sulfate cement of the lower temperature resistance of kind physical strength, raising.
In addition, oneself has found under using polymerizable carboxylic acid Qing Condition, it is live in foamed bricks production process such as acrylic acid
Form the acid of polymerized form (i.e. dimerization, oligomeric and height are poly-).Draw to being added in the mixture of cement composition and monomer acids appropriate
Hair agent obviously increases the degree of the phenomenon.
In addition, in order to further improve the performance of end article and be satisfied different practicalities and desired physical considerations, ability
Other fillers of appropriate form can be added in field technique personnel as needed, such as sand, clay, calcareous mineral, and gravel, aggregate, gently
Aggregate and other slag charges and synthetic material commonly used in the art.
<Foaming product>
The foaming product of the present invention is prepared by foaming raw material, and the foaming raw material is production foaming system in the above method
The various raw materials of product, it is preferable that the foaming product is made using above-mentioned apparatus and method.As previously mentioned, the foaming of the present invention
Product includes a variety of materials, semi-finished product and finished product, preferably cement and foamed bricks made from the foaming raw material.The present invention's
Foaming product may be construction material and building element made of direct processing or secondary operation, such as：Engineering packing material
(such as girt strip), fire-resistant door core filler, fire proofing, interior heat insulating material for external, sound insulation and heat-insulated composite material.Inventor is in reality
It has also been found that the porous material of apparatus and method of the present invention production has particularly suitable as gas and liquid and ion in testing
The absorbent of machine and inorganic material；It has also been found that the porous material is the excellent absorbent for being used as cat litter pad etc..It is of the present invention
The form of foaming product is very more, the above is only and is provided as example.
In one embodiment of the invention, the foaming raw material includes：20~40 parts by weight, preferably 25~35
The flue gas desulfurization glue size of parts by weight, the magnesia of 20~30 parts by weight, preferably 22~28 parts by weight, 6~10 parts by weight, preferably
For the sulfuric acid of 7~8 parts by weight, the slag charge of 15~30 parts by weight, preferably 20~25 parts by weight, 20~40 parts by weight, preferably
The useless ash of 25~35 parts by weight, other additives of 5~20 parts by weight, preferably 10~15 parts by weight.The foaming raw material
Further include foaming component, the foaming component includes foaming agent and air entraining agent, foaming agent consumption be magnesia dosage 3wt%~
10wt%, preferably 5wt%~8wt%, air entraining agent dosage be magnesia dosage 3wt%~10wt%, preferably 5wt%~
8wt%.Preferably, the foaming agent is stearic acid, positive lauric acid/dodecanoic acid or polyacrylic acid；The air entraining agent is detergent alkylate
Sodium sulfonate.The foaming product of the program when specifically for foamed bricks, has excellent physical property, high-strength light, it may have very well
Cost advantage.
Below by embodiment and application examples, the present invention will be further described.Unless specifically stated otherwise, " % " of the invention
Indicate weight percent.Unless specifically stated otherwise, the raw material used in following embodiment and application examples, process conditions explanation be such as
Under：
1, flue gas desulfurization operating mode is referring to following table.
Sintering machine of steel mill flue gas desulfurization project duty parameter
Desulfurizing item emission behaviour
2, other explanations
Desulfurizing agent：Magnesium oxide powder；
The proportioning of desulfurizer slurry is as follows：The weight ratio of desulfurizing agent and water is 1：3；The embodiment that is given below is answered
In use-case, following raw material is used：
--- stearic acid (Aldrich)
--- positive lauric acid/dodecanoic acid (Aldrich)
--- polyacrylic acid (Fluka#81140)
--- neopelex (Aldrich)
--- cetyl sodium sulfosuccinate (Cyanamid)
--- calcined magnesia
--- sulfuric acid
--- flue gas desulfurization glue size comes from Beijing Zhong Jingjiamei environmental science and technology limited liability company in Tianjin Rong Cheng steel
Iron desulfurization waste liquor production scene.Density d=1.25 gram/cc, H2O/MgSO4Than being 3.1.
--- useless ash is acid flyash (AFA), (contains main component from the Shanxi power plants Xiang Kuang：50wt%SiO2,
25wt%Al2O3, 9wt%CaO).
--- blast furnace slag (contains main component from Tianjin Rong Cheng joints Iron And Steel Co., Ltd：50wt%SiO2,
12wt%A12O3, 9wt%Fe2O3, 16wt%CaO).
--- quartz sand (200 mesh) contains 99.5wt%SiO2。
It should illustrate that the purity of workable raw material is not most important.Many outsourcing materials can be used as suitable and cheap
Raw material.
The preparation and experiment of magnesium sulfate foamed bricks are put into the required amount of raw material in Retch grinding machines (model KM-1),
And carry out grinding/hybrid manipulation 20 minutes.Thus be made a kind of stickum, by the substance be put into size be 200 × 240 ×
Stand in the mold of 150mm and at room temperature maintenance 10 days.Maintenance finishes, and the pour mass or press body are exposed to fast rapid-curing cutback
Its water resistance and stability are evaluated in dry/freezing (D/F) cycle.Quick D/F cycles Bao include Yi Xia Bu Sudden：A) dry at 80 DEG C
24 hours；B) it impregnates 24 hours in water；C) freeze to soak body 24 hours at -18 DEG C；And d) Frozen Body is put into boiling water
And it is kept for 4 hours wherein.The reaction of object through so handling shows their water resistance, stability, resistance to heat shocks, water suction
Property, weightless and variable density.Bending strength and compression strength are measured before and after carrying out five cycles described above.
Embodiment 1
The device of the production foaming product of the present invention is as shown in Figure 1.The device includes：Flue gas desulfurization device 1, slurry storage
Equipment 4, magnesia supply arrangement 6, sulfuric acid supply arrangement 7, hybrid process equipment 8, slag charge supply arrangement 9, is given up at consersion unit 5
Grey supply arrangement 10, other additive supply arrangements 11, foaming component supply arrangement 12, drying equipment 13 and packaging facilities 14.
Flue gas desulfurization device 1, which is internally provided with, absorbs spraying zone 2；Consersion unit 5, sulfuric acid supply arrangement 7, mixes magnesia supply arrangement 6
Close process equipment 8, slag charge supply arrangement 9, useless grey supply arrangement 10, additive supply arrangement 11, foaming component supply arrangement 12,
Drying equipment 13 and packaging facilities 14 are all disposed within the outside of flue gas desulfurization device 1.Flue gas desulfurization device 1 and slurry storage device
4 are connected to by discharge pump 3 with pipeline.Slurry storage device 4, consersion unit 5, hybrid process equipment 8, drying equipment 13 and packaging
Equipment 14 is sequentially connected.Magnesia supply arrangement 6 and sulfuric acid supply arrangement 7 are respectively connected to consersion unit 4；Slag charge supply arrangement
9, useless grey supply arrangement 10, other additive supply arrangements 11 and foaming component supply arrangement 12 are respectively connected to hybrid process and set
Standby 8.The concrete structure of each equipment is configured with common sense in the field with reference to the foregoing.
The method using above-mentioned apparatus production foamed bricks is described below：
Desulfurizer slurry-magnesium hydroxide slurry is made by industrial tap water is added in desulfurizing agent magnesium oxide powder, and pumps
Into flue gas desulfurization device 1, for the sulfur dioxide in absorbing spraying zone 2 and absorbing flue gas.
Come from sintering device flue gas (content of sulfur dioxide 2000mg/Nm3, oxygen content 18vt%) and from flue gas desulfurization
The lower part of equipment 1 enters inside flue gas desulfurization device 1.In flue gas uphill process, connect with desulfurizer slurry absorbing spraying zone 2
It touches, flue gas is discharged from 1 top of flue gas desulfurization device.It absorbs spraying zone 2 and sprays desulfurizer slurry to absorb the titanium dioxide in flue gas
Sulphur.
Desulfurizer slurry forms flue gas desulfurization glue size after sulfur dioxide absorption, and (containing magnesium sulfate, temperature is 30 DEG C, density is
1.2t/m3), it is imported into slurry storage device 4 and stores through discharge pump 3.
Above-mentioned flue gas desulfurization glue size enters consersion unit 5 (crystallizer reactive tank), is added in above-mentioned flue gas desulfurization glue size
Magnesia and sulfuric acid, magnesia and sulfuric acid reaction generate magnesium sulfate, to improve the magnesium sulfate concentration in slurries, and institute's oxygenation
It is excessive to change magnesium, finally obtains in magma the weight ratio of magnesium sulfate and magnesia 1.The magma of consersion unit 5 is delivered to mixing
Process equipment 8.
It is 400m by specific surface area is ground into collected from the clinker of steel mill2The powder of/kg is then fed into slag charge supply and sets
Standby 9；Useless grey supply arrangement 10 is added in useless ash from steel mill's coal-burning boiler；The supply of other additives is added in other additives
Equipment 11；Foaming component supply arrangement 12 is added in foaming component.Then, by above-mentioned slag charge, useless ash, other additives, foaming
Component is all sent into be stirred with the magma from consersion unit 5 in hybrid process equipment 8 and be mixed, mixing speed 1600rpm,
Mixing time 30 minutes is to get to magnesium sulfate foamed bricks.Magnesium sulfate foamed bricks are dried through drying equipment 13, and packaging facilities 14 is packed
After be put in storage.
Application examples 1-5
Using the device and technical process production foamed bricks in embodiment 1, it is formulated as follows：
1 foamed bricks component basic components of table
Prepare the dosage such as following table of the foaming component of foamed bricks addition：
The formula of 2 foaming component of table
Mo Ban Zhong Plaster rows by above-mentioned foamed bricks component in 20 × 20 × 20mm are poured into a mould, which is dried/is freezed
Process, the result that test acquisition is carried out by GB/T 177-85 standards are as shown in table 3 below.
3 foamed bricks performance of table
Note：W.A.-water absorption rate；D-density；CS-compression strength；MOR-bending strength.
As seen from table, when the weight ratio of stearic acid/MgO is 5%, the density of the density ratio foamed bricks 3 of foamed bricks 2 is small, says
Bright stearic foaming effect is more preferable, meanwhile, the water absorption rate of foamed bricks 2 and 3 is not much different, due to the foaming effect of foamed bricks 2
More preferably, foamed bricks porosity is larger, causes its compression strength and bending strength that will be less than foamed bricks 3.Foamed bricks 1 and 3 are compared,
Since foamed bricks 1 add, stearic acid is more, and foaming effect is more preferable, so the density and hydrophily of foamed bricks 1 will be less than foaming
Brick 3, the compression strength and bending strength of foamed bricks 1 are then less than foamed bricks 3.Foamed bricks 4 use positive lauric acid/dodecanoic acid as foaming agent, right
Than foamed bricks 3 and 4, the density of foamed bricks 3 is less than foamed bricks 4, illustrates that stearic foaming effect is better than positive lauric acid/dodecanoic acid, and stearic
The hydrophobicity calibration lauric acid/dodecanoic acid of acid is eager to excel, so the water absorption rate of foamed bricks 3 is less than foamed bricks 4, the foaming effects of foamed bricks 3 compared with
It is good, cause its compression strength and bending strength low compared with 4.Foaming agent used in foamed bricks 5 is polyacrylic acid, due to the water of polyacrylic acid
Dissolubility is preferable, so the water absorption rate of foamed bricks 5 is maximum, but the foaming effect of polyacrylic acid is poor, thus the density of foamed bricks 5 compared with
Greatly, since foaming effect is bad, so aperture is smaller, hole wall is thicker, and compression strength and bending strength are preferable.Above each foamed bricks
Performance it is each has something to recommend him, it is overall all good.In general, 3 each index equilibrium of foamed bricks is preferable, has high quality, low-density
The characteristics of, good physical properties are more satisfactory foaming products.
Present invention is not limited to the embodiments described above, without departing from the essence of the present invention, this field 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 process units of foaming product, which is characterized in that including：
Flue gas desulfurization device for removing the sulfur dioxide in flue gas using magnesium oxide method, and forms flue gas desulfurization glue size, described
Flue gas desulfurization glue size in contain magnesium sulfate；
Slurry storage device for storing the flue gas desulfurization glue size from flue gas desulfurization device, and flue gas desulfurization glue size is conveyed
To consersion unit；
Consersion unit, for receiving the flue gas desulfurization glue size from slurry storage device, and by into the flue gas desulfurization glue size
Sulfuric acid and magnesia are added to improve the magnesium sulfate concentration of the flue gas desulfurization glue size, to form magma, is contained in the magma
Magnesium sulfate crystals；
Magnesia supply arrangement, for providing foaming product magnesia；
Sulfuric acid supply arrangement, for providing foaming product sulfuric acid；
Useless ash supply arrangement, for providing foaming product with useless ash；
Slag charge supply arrangement, for providing foaming product slag charge；
Foaming component supply arrangement, for providing foaming component；
Other additive supply arrangements, for providing foaming product other additives, other described additives do not include useless
Ash, slag charge and foaming component；
Hybrid process equipment, for magma, the magnesia from magnesia supply arrangement of autoreaction equipment in future, from useless ash
Useless ash, the foaming product slag charge from slag charge supply arrangement, the foaming product from additive supply arrangement of supply arrangement
With other additives and from the foaming component hybrid process of foaming component supply arrangement, to form foaming product；
Wherein, the slurry storage device, consersion unit, magnesia supply arrangement, sulfuric acid supply arrangement, useless grey supply arrangement,
Slag charge supply arrangement, other additive supply arrangements, foaming component supply arrangement and hybrid process equipment are respectively positioned on the flue gas
The outside of desulphurization plant.
2. the apparatus according to claim 1, which is characterized in that the top in the flue gas desulfurization device, which is equipped with to absorb, sprays
Area is drenched, for removing the sulfur dioxide in flue gas using magnesium oxide method, and forms flue gas desulfurization glue size.
3. the apparatus according to claim 1, which is characterized in that described device further includes slag charge milling apparatus, for that will send out
Brewage is ground to powder with slag charge, and is delivered to slag charge supply arrangement.
4. according to claims 1 to 3 any one of them device, which is characterized in that the process units of the foaming product is
Produce the device of foamed bricks.
5. a kind of method producing foaming product using 4 any one of them device of Claims 1 to 4, includes the following steps：
1) flue gas desulfurization step：Using the sulfur dioxide in magnesium oxide method removing flue gas in flue gas desulfurization device, and form cigarette
Desulfurization slurries contain magnesium sulfate in the flue gas desulfurization glue size；
2) step is discharged in slurries：The flue gas desulfurization glue size of flue gas desulfurization device is expelled to slurry storage device；
3) reaction step：The flue gas desulfurization glue size from slurry storage device is received in consersion unit, and to the flue gas desulfurization
Sulfuric acid and magnesia are added in slurries to improve the magnesium sulfate concentration of the flue gas desulfurization glue size, to form magma, the magma
In contain magnesium sulfate crystals；
4) hybrid process step：In hybrid process equipment future autoreaction equipment magma, from magnesia supply arrangement
Magnesia, the useless ash from useless grey supply arrangement, the foaming product slag charge from slag charge supply arrangement, from other additives
Other additives of the foaming product of supply arrangement and foaming component hybrid process from foaming component supply arrangement, to be formed
Foaming product.
6. according to the method described in claim 5, it is characterized in that, in step 3), magnesium sulfate and magnesia in the magma
Weight ratio is 0.8~1.2:1.
7. method according to claim 5 or 6, which is characterized in that in step 4),
The slag charge be selected from clinker, slag, steel slag and iron slag it is one or more；
The useless ash is one or more in flyash, land plaster, dolomite dust, shale powder；
Other described additives include one or more selected from following additive：Stearic acid, calcium stearate, zinc stearate, silicon
Rubber, polyester fiber, glass fibre, phosphoric acid, dihydric phosphate, dibasic alkaliine, tartaric acid, tartrate and amino trimethylene first
Base phosphonic acids, polypropylene, polyacrylonitrile, lignin, hydroxypropyl methyl cellulose or siloxanes；
The foaming component includes organic foaming agent or inorganic foaming agent；The organic foaming agent is selected from organic carboxyl acid, organic
The acid anhydrides of carboxylic acid or monocarboxylate it is one or more；The inorganic foaming agent is selected from sodium bicarbonate or ammonium carbonate.
8. the method according to the description of claim 7 is characterized in that the foaming component further includes air entraining agent, the bleed
Agent be selected from the rosin resin of saponification, Wen Shaer resins, saponification spit your oil, dodecyl sodium sulfate, neopelex,
It is one or more in the sulfonated salts of oil hydroxyl.
9. according to the method described in claim 5, it is characterized in that：
The foaming component includes foaming agent and air entraining agent, and foaming agent consumption is the magnesia dosage from magnesia supply arrangement
3wt%~10wt%, air entraining agent dosage be the magnesia dosage from magnesia supply arrangement 3wt%~10wt%.
10. according to the method described in claim 9, it is characterized in that, the foaming agent is stearic acid, positive lauric acid/dodecanoic acid or poly- third
Olefin(e) acid；The air entraining agent is neopelex.
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| CN201810414904.7A CN108373315B (en) | 2015-08-19 | 2015-08-19 | Device and method for producing magnesium sulfate foamed bricks by magnesium desulfurization methods |
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| CN106467387A (en) | 2017-03-01 |
| CN106467387B (en) | 2018-12-21 |
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