CN107902663A - Utilize the method and device of industrial silicon by-product SILICA FUME and waste heat production waterglass - Google Patents
Utilize the method and device of industrial silicon by-product SILICA FUME and waste heat production waterglass Download PDFInfo
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- CN107902663A CN107902663A CN201711439357.XA CN201711439357A CN107902663A CN 107902663 A CN107902663 A CN 107902663A CN 201711439357 A CN201711439357 A CN 201711439357A CN 107902663 A CN107902663 A CN 107902663A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention discloses a kind of method and device using industrial silicon by-product SILICA FUME and waste heat production waterglass, the method is heat source using smelting industrial silicon flue gas using the SILICA FUME after roasting as silicon source, and high-purity waterglass is produced by liquid phase method；Described device includes separative element, roasting unit, reaction member, heat exchange cooling unit, filter element and waste heat recovery unit, produces using described device and according to the method described above high-purity waterglass.SILICA FUME is first passed through the volatile impurity in roasting removing SILICA FUME by the present invention, then waste gas residual heat is made full use of to carry out liquid phase reactor, water produced glass water white transparency, modulus are high and purity is high, rational technology, high conversion rate and cost are low, solves dust pollution question, added value is improved, there is good economic and social benefit.
Description
Technical field
The invention belongs to the technical field of liquid soluble glass production, more particularly, is related to one kind and utilizes industrial silicon by-product
The method and device of SILICA FUME and waste heat production waterglass.
Background technology
SILICA FUME is in industrial silicon or Antaciron production process, SiO the and Si gases produced in ore-smelting electric furnace escape
And the siliceous industrial fine dust formed by air rapid oxidation, cooling, it is micron order fine powder and dioxide-containing silica height, by people
It is big to body harm after suction, belong to solid waste.With the reinforcement of national environmental protection dynamics, in industrial silicon production enterprise flue gas
SILICA FUME begin through environment protection cloth bag cleaner and be collected, to reach qualified discharge；And the flue gas emission containing SILICA FUME
Temperature is up to 500~650 DEG C, even up to 900 DEG C sometimes, is run for protection cloth bag in safe temperature range, most of enterprises
Industry is all to install an aerial cooler additional before bag filter to carry out air radiating and cooling, is then down to 200 DEG C of left sides in flue gas
The right bag filter that enters collects SILICA FUME, and the exhaust gas volumn is huge so that aerial cooler cost is high, and final big calorimetric
It can scatter and disappear in air, not be utilized effectively.
SiO in the SILICA FUME collected in smelting industrial silicon flue gas2Content can be used as mixing in theory generally 90~98.2%
Solidifying soil raw material, refractory material, have preferable corrosion resistance, insulating properties, wearability, impermeability, frost resistance, heat-resisting quantity,
Packing material available for organic compounds such as rubber, resins.But because of the characteristic of industrial silicon production, negative pressure, flue gas temperature in its stove
Degree has fluctuation, thus the SILICA FUME content in its flue gas is very unstable, direct applied mechanical property and not good enough, the reality of SILICA FUME
Border addition ratio is seldom, acts on unobvious, and practical application amount is very limited, and substantial amounts of SILICA FUME is hoarded, market digestive difficulties,
The big obstacle for restricting the clean environment firendly production of industrial silicon enterprise is become.
SiO in industrial silicon SILICA FUME2In amorphous state undefined structure, content is up to 90~98.2%, with crystalline state SiO2Than
Compared with, its chemical reactivity higher, granularity is tiny in addition, and surface area is big, and the reactivity in alkaline solution is very strong, therefore,
High-quality potassium is prepared using this SILICA FUME as raw material, sodium silicate is that industrial silicon solid waste turns waste into wealth and reduce dust secondary pollution
There is the approach of removing.
Waterglass is a kind of widely used inorganic chemical industry basic material.Its principal item has potassium water glass and sodium water glass
Glass, production method are divided into two kinds of solid phase high-temperature melting method and liquid phase method, wherein solid phase high-temperature melting method be with crystalline state quartz sand and
The frit reaction in 1400~1500 DEG C of high-temperature molten stove of sodium carbonate (potassium) or sodium sulphate (potassium) is made, its advantage is can be according to need
The waterglass product of different moduluses is prepared, the drawback is that energy consumption is big, exhaust gas environmental protection treatment is costly and the raw material such as quartz sand
In metal impurities all incorporated in product.Liquid phase rule is to use the temperature of sodium hydroxide solution and quartz sand at 130~160 DEG C
Spend, react obtained under the reaction pressure of 0.3~0.63MPa, advantage is that energy consumption is lower with respect to the former, and shortcoming is the waterglass of production
Modulus is low and alkaline consumption is big.
In conclusion problem existing in the prior art is：
1st, existing production waterglass technology is limited to respective raw material sources, specific process conditions, otherwise focus on product mould
Several raisings, or focusing on energy consumption, cost reduction, or focusing on the raising of product purity, fails well while accomplishes to produce
Waterglass cost is low, product modulus is high, purity is high.
2nd, SILICA FUME prepares waterglass in the prior art, and used SILICA FUME is unprocessed, institute's sulfur-bearing, phosphorus, carbon and
The harmful components such as hydrocarbon oxygen compound can enter in waterglass and filter residue prepared by reaction, make waterglass colourity depth, have peculiar smell, have
Evil component is more, belongs to low side waterglass product, can not be applied to high-end product, and filter residue more easily causes secondary pollution.
The content of the invention
In order to solve the problems in the existing technology, the object of the present invention is to provide one kind using industrial silicon SILICA FUME and
Exhaust gas heat source liquid phase method produces the method and device of high-purity waterglass, by removing the organic volatiles such as coal tar in SILICA FUME, carbon
Part come avoid its to subsequent product production and quality influence and make full use of fume waste heat to react, effectively utilize industry
Silicon silicon powder realizes the industrialized production of waterglass product, at the same realize production waterglass cost is low, product modulus is high, pure
Spend high effect.
An aspect of of the present present invention provides the method using industrial silicon by-product SILICA FUME and waste heat production waterglass, the side
Method comprises the following steps：
The high temperature SILICA FUME that thermal release is collected from smelting industrial silicon flue gas is carried out to the high temperature under oxygen-enriched atmosphere A,
Roasting obtains roasting SILICA FUME；
B, the roasting SILICA FUME is added in reaction kettle together with liquid sodium hydroxide/liquid potassium hydroxide and water and stirred
It is uniformly mixed and high temperature waterglass mother liquor is obtained using smelting industrial silicon flue gas as heat source response；
C, the high temperature waterglass mother liquor cooled and filtered is obtained into high-purity waterglass.
According to the present invention using industrial silicon by-product SILICA FUME and one embodiment of the method for waste heat production waterglass, in step
In rapid A, using cyclone separator, thermal release collects to obtain high temperature SILICA FUME, the high temperature SILICA FUME from smelting industrial silicon flue gas
Temperature be 560~650 DEG C；It is 720~1100 DEG C to control calcination temperature, and roasting time is 15~90 minutes；The roasting is micro-
Non-volatile part in silica flour.
According to the present invention using industrial silicon by-product SILICA FUME and one embodiment of the method for waste heat production waterglass, in step
In rapid B, SiO is controlled2:NaOH/KOH:H2The mass ratio of O is 2~2.7:1:3~9.5；Controlling reaction temperature is 165~210 DEG C,
Preferably 170~200 DEG C, more preferably 175~190 DEG C；It is 60~360 minutes to control the reaction time, is preferably 120~300
Minute, more preferably 180~240 minutes.
According to the present invention using industrial silicon by-product SILICA FUME and one embodiment of the method for waste heat production waterglass, in step
In rapid B, afterheat steam heating mixed material is passed through into reaction kettle and is reacted, wherein, in waste heat boiler by water with from work
The recycling waste heat of the high-temperature flue gas heat exchange after SILICA FUME is isolated in industry silicon flue gas during smelting and obtains the afterheat steam, waste heat steams
The pressure of vapour is 1~3MPa, temperature is 220~450 DEG C.
According to the present invention using industrial silicon by-product SILICA FUME and one embodiment of the method for waste heat production waterglass, in step
In rapid C, the high temperature waterglass mother liquor is cooled to room temperature~80 DEG C using pipe heat exchanger, is preferably cooled to 40~80
DEG C, more preferably it is cooled to 50~60 DEG C；Waterglass mother liquor is carried out using rotary vacuum filter or filter press high purity water glass is obtained by filtration
Glass.
It is described according to the present invention using industrial silicon by-product SILICA FUME and one embodiment of the method for waste heat production waterglass
Method is further included carries out the recycling of dedusting again and by more than part by obtained low-temperature flue gas after high-temperature flue gas recycling waste heat
Hot steam again recovery waste heat the step of, wherein, low-temperature flue gas progress dedusting is recycled to obtain fine silicon powder and qualified tail
The fine silicon powder is simultaneously returned and high-temperature roasting is carried out together with high temperature silicon powder by gas, and part of waste heat steam is used to generate electricity and is incited somebody to action
Gained electric energy is used to roast high temperature silicon powder.
It is described according to the present invention using industrial silicon by-product SILICA FUME and one embodiment of the method for waste heat production waterglass
It is high-purity waterglass water white transparency, tasteless；When high-purity waterglass is sodium silicate, mass concentration is in more than 21.0wt%, dioxy
For SiClx content in more than 15.5wt%, iron content is less than 10ppm, and aluminium content is less than 25ppm, and content of beary metal is less than 3ppm, mould
Number is 3~3.4；When high-purity waterglass is potassium water glass, mass concentration exists in more than 22.5wt%, dioxide-containing silica
More than 15.5wt%, iron content are less than 10ppm, and aluminium content is less than 25ppm, and content of beary metal is less than 3ppm, modulus for 3.4~
3.8。
Another aspect provides it is a kind of using industrial silicon by-product SILICA FUME and waste heat production waterglass method,
Waterglass, institute are produced using described device and according to the above-mentioned method using industrial silicon by-product SILICA FUME and waste heat production waterglass
Stating device includes separative element, roasting unit, reaction member, heat exchange cooling unit, filter element and waste heat recovery unit；
The smoke inlet of the separative element is connected with industrial silicon exhaust system, the cigarette of exhanst gas outlet and waste heat recovery unit
The material inlet of the connection of gas entrance, material outlet and roasting unit connects；
The material outlet of the roasting unit and the material inlet of reaction member connect；
The material outlet of the reaction member is connected with the material inlet for the cooling unit that exchanges heat, thermal source inlet and Waste Heat Recovery
The steam (vapor) outlet connection of unit；
The material outlet of the heat exchange cooling unit and material inlet connection, cooling water inlet and the water source of filter element connect
Connect, the material inlet of hot water outlet and reaction member connects.
It is described according to the present invention using one embodiment of industrial silicon by-product SILICA FUME and the device of waste heat production waterglass
Separative element is cyclone separator or bag filter, and the roasting unit is roaster, and the reaction member is reaction kettle, institute
It is pipe heat exchanger to state heat exchange cooling unit, and the filter element is rotary vacuum filter or filter press, and the waste heat recovery unit is remaining
Heat boiler.
It is described according to the present invention using one embodiment of industrial silicon by-product SILICA FUME and the device of waste heat production waterglass
Device further includes recovery unit, and the recovery unit includes off-gas recovery subelement and waste heat recovery subelement；
The waste heat recovery subelement is generator, and the steam inlet of the generator and the steam of waste heat recovery unit go out
Mouth connects and the generator is powered directly to roasting unit；
The connection of the exhanst gas outlet of the smoke inlet of the off-gas recovery subelement and waste heat recovery unit, exhanst gas outlet with it is big
The material inlet of gas connection, material outlet and roasting unit connects, and the off-gas recovery subelement includes sequentially connected cloth bag
Dust settler and desulphurization denitration device.
Compared with prior art, the present invention eliminates wherein using industrial silicon by-product SILICA FUME as silicon source and by calcination process
Most of objectionable impurities, further activate SILICA FUME, guarantee provided for the raising of waterglass quality；Meanwhile present invention profit
It is the energy with industrial silicon flue gas during smelting, the steam and electric power provided using smoke and waste steam boiler and cogeneration, can expire completely
The needs of sufficient liquid phase method waterglass production, the discarded energy of effective recycling, reduce production cost；Pass through micro- silicon of roasting
Powder reacts the liquid sodium silicate of production or the modulus height of potassium water glass, purity with sodium hydroxide or potassium hydroxide solution liquid phase method
Height, added value of product is than improving 50~120%；This technique is easy to industrialize, and solves industrial silicon clean environment firendly production energy-saving
Technology barrier, high mode, high-purity sodium are prepared for industrial silicon recycling SILICA FUME and exhaust gas heat source and efficient, low cost
(potassium) waterglass provides a kind of brand-new method.
Brief description of the drawings
Fig. 1 is shown produces waterglass using industrial silicon by-product SILICA FUME and waste heat according to an exemplary embodiment of the present
The process flow chart of method.
Fig. 2 is shown produces waterglass using industrial silicon by-product SILICA FUME and waste heat according to an exemplary embodiment of the present
The structure diagram of device.
Embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification, unless specifically stated, can be equivalent by other or with similar purpose
Alternative features are replaced.I.e., unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
.
The present invention be using the SILICA FUME after roasting as silicon source, while using smelting industrial silicon flue gas be heat source, pass through liquid phase
Method produces to obtain high-purity waterglass.
Industrial silicon by-product SILICA FUME of the present invention is in industrial silicon or Antaciron production process, in ore-smelting electric furnace
SiO the and Si gases effusion of interior generation and the siliceous industrial fine dust formed by air rapid oxidation, cooling.After testing, lead to
The fugitive constituent crossed in the SILICA FUME of smelting industrial silicon fume collection is 1.62~4.78wt%, and the main component in fugitive constituent is coal
Tar and carbon dust.The fugitive constituent causes one layer of oily gelling thing of formation in the liquid after reaction, increases filtration resistance and part
Dissolve in liquid soluble glass, make waterglass colored and with serious peculiar smell；Second, SILICA FUME granularity is too thin so that reaction system
Water distribution quantity it is big, otherwise reaction system viscosity is big and be unfavorable for reacting, thus causes final strength of fluid low, while not anti-
The fine silicon powder answered forms more fine and close sediment with coal tar, carbon dust, it is difficult to filters.
For the above problem found, the present invention removes the fugitive constituent in SILICA FUME by the method for oxygen-enriched high-temperature roasting
(mainly coal tar and carbon dust), while SILICA FUME is occurred so as to increase SILICA FUME density and granularity by sintering by high temperature, have
Effect reduces the reaction water consumption of subsequent applications, improves end reaction liquid concentration, and under conditions of its reactivity is ensured
Substantially increase the filter efficiency of liquid.Most of all, being handled by aforesaid way SILICA FUME and then by gained
Roasting SILICA FUME is used to prepare waterglass, and the waterglass water white transparency and modulus react, filtered out is high, purity is high, can be production
The follow-up extensive use and high-end market application of product lay the foundation.
First the method using industrial silicon by-product SILICA FUME and waste heat production waterglass of the present invention is carried out specifically below
It is bright.
Fig. 1 is shown produces waterglass using industrial silicon by-product SILICA FUME and waste heat according to an exemplary embodiment of the present
The process flow chart of method.As shown in Figure 1, exemplary embodiment according to the present invention, the industrial silicon SILICA FUME removal of impurities activation
Method specifically include following steps.
Step A：SILICA FUME separating and collecting and roasting
The high temperature high temperature SILICA FUME that thermal release is collected from smelting industrial silicon flue gas carried out under oxygen-enriched atmosphere roasts
Burning obtains roasting SILICA FUME.
Wherein it is preferred to which thermal release collects to obtain SILICA FUME from smelting industrial silicon flue gas using cyclone separator, this is micro-
Silica flour is the high temperature SILICA FUME that temperature is 560~650 DEG C, which is directly roasted, and is conducive to save the energy.
Specifically, which can be continuously introduced into roaster and roast and continuous discharge after baking, roasting process
In be continually fed into oxygen-enriched air or purity oxygen and form oxygen-enriched atmosphere, wherein SILICA FUME preferably with the dynamical fashion that is continuously introduced into
Row roasting.Thus, dynamic SILICA FUME can sufficiently uniformly be contacted with the oxygen-enriched air or purity oxygen being continually fed into, and herein
The fugitive constituents such as the coal tar and carbon dust that are allowed under oxygen-enriched hot environment in SILICA FUME obtain promptly combustion decomposition and release substantial amounts of
Thermal energy, the thermal energy can keep the high temperature in roaster, suitably save part heating energy source, so that SILICA FUME is roasting
Continuous high temperature is kept in stove.Also, it is 720~1100 DEG C that the temperature in roaster is controlled by additional heat source, roasting time
Control was achieved in sufficient fugitive constituent and decomposes at 15~90 minutes.Wherein, roaster can be fluidizing reactor, revolution roasting
Stove or microwave baking furnace are burnt, the heat source of roaster can be natural gas, coal, electricity or microwave.
According to a preferred embodiment of the invention, it is 850~1100 DEG C to preferably control the calcination temperature in roaster, roasting
Time is 15~50 minutes；It is 900~1000 DEG C more preferably to control the calcination temperature in roaster, and roasting time is 18~40
Minute；It is 920~950 DEG C most preferably to control the calcination temperature in roaster, and roasting time is 20~30 minutes.
Calcination process is carried out to SILICA FUME under above-mentioned temperature and time condition and dynamic condition, first, can be by micro- silicon
The abundant combustion decomposition of the organic volatile part such as coal tar, carbon in powder, second, micro- silicon of exquisiteness can be made while high-temperature roasting
Powder sinters, and formation small porous particle, granularity is thicker and increase in density, beneficial to subsequent reactions.
After testing, the fugitive constituents such as coal tar and carbon dust are not contained in the roasting SILICA FUME after roasting.
Step B：Liquid phase reactor
The roasting SILICA FUME that step A is obtained is added into reaction kettle together with liquid sodium hydroxide/liquid potassium hydroxide and water
In be uniformly mixed and obtain high temperature waterglass mother liquor using smelting industrial silicon flue gas as heat source into reaction.Wherein, liquid hydrogen
Sodium oxide molybdena can be liquid caustic soda or the sodium hydroxide solution being configured to using solid sodium hydroxide, the mass concentration of liquid sodium hydroxide
Preferably 30~50wt%, liquid potassium hydroxide are similar therewith.
Specifically, the present invention is reacted by being passed through afterheat steam heating mixed material into reaction kettle, wherein, remaining
Water is obtained with isolating the high-temperature flue gas heat exchange recycling waste heat after SILICA FUME from smelting industrial silicon flue gas in heat boiler
The afterheat steam, the pressure of afterheat steam is 1.0~3.0MPa, temperature is 220~450 DEG C.Waste heat boiler can control flue gas
Temperature is down to 200 DEG C or so from 500~650 DEG C, it is ensured that low-temperature flue gas temperature below can in cloth bag operational envelope,
An afterheat steam part caused by waste heat boiler is used for subsequent reactions and heats, and a part, which can be used for generating electricity and provide part, to be moved
Power.
In this step, SiO is controlled2:NaOH/KOH:H2The mass ratio of O is 2~2.7:1:3~9.5；Controlling reaction temperature
It is preferably 170~200 DEG C for 165~210 DEG C, more preferably 175~190 DEG C；It is 60~360 minutes to control the reaction time, excellent
Elect as 120~300 minutes, more preferably 180~240 minutes.High temperature waterglass mother liquor is obtained after reaction.During the reaction,
Reaction can be controlled by the way of insulation or pressurize.
Step C：Cold filtration
High temperature waterglass mother liquor cooled and filtered is obtained into high-purity waterglass.
Specifically, high temperature waterglass mother liquor can be cooled to room temperature~80 DEG C using pipe heat exchanger, preferably cooled down
To 40~80 DEG C, 50~60 DEG C are more preferably cooled to.Then, rotary vacuum filter or filter press can be used to carry out waterglass mother liquor
High-purity waterglass is obtained by filtration.
It is high-purity waterglass water white transparency, tasteless；When high-purity waterglass is sodium silicate, mass concentration 20.0wt% with
On, for dioxide-containing silica in more than 15.5wt%, iron content is less than 10ppm, and aluminium content is less than 25ppm, and content of beary metal is less than
3ppm, modulus are 3~3.4；When high-purity waterglass is potassium water glass, mass concentration contains in more than 22.5wt%, silica
Amount is in more than 15.5wt%, and iron content is less than 10ppm, and aluminium content is less than 25ppm, and content of beary metal is less than 3ppm, modulus 3.4
~3.8.
The low-temperature flue gas obtained after high-temperature flue gas recycling waste heat is carried out as shown in Figure 1, the method for the present invention further includes
Again dedusting recycling and by part of waste heat steam again recovery waste heat the step of.Wherein, low-temperature flue gas progress dedusting is recycled
To fine silicon powder and qualified tail gas (passing through denitration desulfurization process), and fine silicon powder is returned height is carried out together with high temperature silicon powder
Temperature roasting, part of waste heat steam is used to generate electricity and is used to roast high temperature silicon powder by gained electric energy supply roaster.
Waterglass filter efficiency height of the present invention using above-mentioned roasting SILICA FUME by liquid phase method reaction production, liquid after filter
Water white transparency；At the same time using smoke heat energy high efficiency, prepare at low cost high-purity, high-quality, different modulus waterglass, energy
Enough industrialized productions for smoothly realizing SILICA FUME waterglass.
Present invention also offers a kind of using industrial silicon by-product SILICA FUME and the device of waste heat production waterglass, preferably adopt
Produce with the device and according to the method described above waterglass.
Fig. 2 is shown produces waterglass using industrial silicon by-product SILICA FUME and waste heat according to an exemplary embodiment of the present
The structure diagram of device.As shown in Fig. 2, the device includes separative element 10, roasting unit 20, reaction member 30, heat exchange cooling
Unit 40, filter element 50 and waste heat recovery unit 60.
According to the present invention, the smoke inlet of separative element 10 is connected with industrial silicon exhaust system, exhanst gas outlet and waste heat return
Receive the smoke inlet connection of unit 60, the material inlet of material outlet and roasting unit 20 connects.Thus, smelting industrial silicon flue gas
It is directly entered isolated high temperature SILICA FUME in separative element 10 and is given up with high-temperature flue gas, high-temperature flue gas by exhanst gas outlet entrance
Waste Heat Recovery is carried out in heat recovery units 60, high temperature SILICA FUME, which then enters in roasting unit 20, to be roasted.
The material outlet of roasting unit 20 is connected with the material inlet of reaction member 30.Thus, SILICA FUME is roasted to enter instead
Answer in unit 30 and generate high temperature waterglass mother liquor with liquid sodium hydroxide/potassium hydroxide and water hybrid reaction.
The material outlet of reaction member 30 is connected with the material inlet for the cooling unit 40 that exchanges heat, thermal source inlet and Waste Heat Recovery
The steam (vapor) outlet connection of unit 60.Thus, the high temperature waterglass mother liquor obtained after reaction, which enters in heat exchange cooling unit 40, to carry out
Heat exchange cooling obtains cooling waterglass mother liquor, and waste heat recovery unit 60 recycles the afterheat steam that waste heat obtains and enters reaction member 30
In for liquid phase reactor provide thermal energy.
The material outlet of heat exchange cooling unit 40 is connected with the material inlet of filter element 50, cooling water inlet and water source connect
Connect, the material inlet of hot water outlet and reaction member 30 connects.Thus, cooling waterglass mother liquor after cooling is by being obtained by filtration
High-purity waterglass, the media for heat exchange water of heat exchange cooling unit 40 can be used for the liquid phase reactor of next round.
Exemplary embodiment according to the present invention, above device further include recovery unit, which returns including flue gas
Receive subelement 80 and waste heat recovery subelement 70, off-gas recovery subelement 80 is used to recycle the fine silicon powder in low-temperature flue gas and right
Flue gas carries out final process, and waste heat recovery subelement 70 is then used to carry out heat recovery recycling to part of waste heat steam.
Specifically, waste heat recovery subelement 70 can be generator, the steam inlet of generator and waste heat recovery unit 60
Steam (vapor) outlet connection and generator power directly to roasting unit 20 or give other assemblies power supply.Off-gas recovery subelement 80
Smoke inlet be connected with the exhanst gas outlet of waste heat recovery unit 60, exhanst gas outlet and atmosphere, material outlet and roasting it is single
The material inlet connection of member 20, thus the flue gas after processing can be directly discharged into air, and the thin silicon powder that recycling obtains can
Continue roasting and subsequent reactions to return.
In addition, the separative element 10 of the present invention can be cyclone separator or bag filter, roasting unit 20 can be
Roaster, reaction member 30 can be reaction kettle, and heat exchange cooling unit 40 can be pipe heat exchanger, and filter element 50 can be
Rotary vacuum filter or filter press, waste heat recovery unit 70 can be waste heat boiler, and off-gas recovery subelement 80 can include being sequentially connected
Cloth bag dust settler and desulphurization denitration device.However, the present invention is not limited thereto, as long as the device of corresponding function can be realized.
Method with reference to specific embodiment to the present invention using industrial silicon by-product SILICA FUME and waste heat production waterglass
And device is described further.
Wherein, embodiment 1 to 4 carries out the preparation of waterglass using the device of connection mode and action principle shown in Fig. 2.
Embodiment 1：
The high temperature SILICA FUME that thermal release goes out from smelting industrial silicon flue gas is added in roaster and is roasted, removes volatilization
SiO is obtained after part2Content is the roasting SILICA FUME of 97.0wt%, is by roasting SILICA FUME 24.75Kg, mass concentration
The liquid sodium hydroxide 33.5Kg and water 65Kg of 30wt% is added in the 200L reaction kettles of belt stirrer and is mixed evenly, directly
The afterheat steam heating mixed material that pressure is 3.0MPa, temperature is 450 DEG C is passed through, controlling reaction temperature is 175 DEG C, and stirring turns
Speed is 85r/min, and pressurize is reacted 180 minutes, and maximum temperature reaches 195 DEG C in reaction kettle after exothermic heat of reaction, reaction generation high temperature
Waterglass mother liquor.After discharge through heat exchange cool to 55 DEG C when, filtered with rotary vacuum filter, filtration time 5 minutes, obtain it is colourless,
The high-purity sodium silicate of tasteless, transparent liquid.
Analyzed through analysis by titration in industrial silicon sodium GB/T4209-2008 standards, the SiO in the high-purity sodium silicate of gained2
Content is 17.10wt%, Na2O content is 5.69wt%, modulus 3.10；Through 722 spectrophotometric analysis, Fe therein contains
Measure and do not detected for 3ppm, Al content 12ppm, heavy metal；Silica conversion ratio reaches 85.5wt%.
Embodiment 2：
The high temperature SILICA FUME that thermal release goes out from smelting industrial silicon flue gas is added in roaster and is roasted, removes volatilization
SiO is obtained after part2Content is the roasting SILICA FUME of 95.32wt%, by 4 tons of the roasting SILICA FUME, mass concentration 30wt%
12 tons of addition belt stirrers of 5 tons of liquid sodium hydroxide and water 25m3It is mixed evenly in reaction kettle, is passed directly into pressure
Mixed material is heated for the afterheat steam that 3.0MPa, temperature are 450 DEG C, controlling reaction temperature is 185 DEG C, speed of agitator 85r/
Min, insulation reaction 240 minutes, reaction generation high temperature waterglass mother liquor.When cooling after discharge through heat exchange to 60 DEG C, with pressure
Filter filters, and filtration time 26 minutes, obtains the high-purity sodium silicate of colourless, tasteless, transparent liquid.
Analyzed through analysis by titration in industrial silicon sodium GB/T4209-2008 standards, the SiO in the high-purity sodium silicate of gained2
Content is 16.42wt%, Na2O content is 5.12wt%, modulus 3.31；Through 722 spectrophotometric analysis, Fe therein contains
Measure and do not detected for 5ppm, Al content 8ppm, heavy metal；Silica conversion ratio reaches 89.4wt%.
Embodiment 3：
The high temperature SILICA FUME that thermal release goes out from smelting industrial silicon flue gas is added in roaster and is roasted, removes volatilization
SiO is obtained after part2Content is the roasting SILICA FUME of 98.2wt%, is by roasting SILICA FUME 41.3Kg, mass concentration
The liquid sodium hydroxide 48Kg and water 110Kg of 30wt% is added in the 200L reaction kettles of belt stirrer and is mixed evenly, directly
The afterheat steam heating mixed material that pressure is 3.0MPa, temperature is 450 DEG C is passed through, controlling reaction temperature is 190 DEG C, and stirring turns
Speed is 85r/min, and insulation reaction 240 minutes, reacts generation high temperature waterglass mother liquor.Cool after discharge through heat exchange to 75 DEG C
When, filtered with rotary vacuum filter, filtration time 9 minutes, obtains the high-purity sodium silicate of colourless, tasteless, transparent liquid.
Analyzed through analysis by titration in industrial silicon sodium GB/T4209-2008 standards, the SiO in the high-purity sodium silicate of gained2
Content is 19.15wt%, Na2O content is 5.82wt%, modulus 3.40；Through 722 spectrophotometric analysis, Fe therein is not
Detection, Al content 12ppm, heavy metal do not detect；Silica conversion ratio reaches 86.4wt%.
Embodiment 4：
The high temperature SILICA FUME that thermal release goes out from smelting industrial silicon flue gas is added in roaster and is roasted, removes volatilization
SiO is obtained after part2Content is the roasting SILICA FUME of 98.2wt%, by roasting SILICA FUME 34Kg, mass concentration 30wt%
Liquid sodium hydroxide 50Kg and water 110Kg add belt stirrer 200L reaction kettles in be mixed evenly, be passed directly into pressure
The afterheat steam heating mixed material that power is 3.0MPa, temperature is 450 DEG C, controlling reaction temperature is 190 DEG C, is reacted 240 minutes,
Reaction generation high temperature waterglass mother liquor.When cooling after discharge through heat exchange to 80 DEG C, filtered with rotary vacuum filter, filtration time 11 divides
Clock, obtains the high-purity potassium water glass of colourless, tasteless, transparent liquid.
Through titrimetry principle analysis in GB/T4209-2008 standards, the SiO in the high-purity potassium water glass of gained2Content is
16.06wt%, K2O content is 6.617wt%, modulus 3.80；Through 722 spectrophotometric analysis, Fe therein is not detected, Al
Content is 12ppm, and heavy metal does not detect；Silica conversion ratio reaches 90.18wt%.
Comparative example 1：
Its SiO is detected after the high temperature SILICA FUME cooling being directly separated out from smelting industrial silicon flue gas2Content is
94.5wt%, fugitive constituent 3.21wt%, does not roast it, directly with SILICA FUME 24.75Kg, mass concentration 30wt%
Liquid sodium hydroxide 33.5Kg and water 65Kg add belt stirrer 200L reaction kettles in be mixed evenly, be passed directly into pressure
The afterheat steam heating mixed material that power is 3.0MPa, temperature is 450 DEG C, controlling reaction temperature is 175 DEG C, speed of agitator 85r/
Min, pressurize reaction, when reacting to 48 minutes, reaction kettle stirring beginning is slack-off, and goes out stirring motor and show electromagnetic noise, is driven skin
Belt wheel skids, and at 55 minutes, speed of agitator is down to about 34r/min, by adjusting motor speed, driving belt skid it is more serious,
190 DEG C of reaction temperature at this time, after reaction mass temperature reduced to 150 DEG C by the outer cooling that exchanges heat, speed of agitator recovers, then reacts
After 15 minutes, temperature is raised to 173 DEG C, and agitation revolution starts slack-off again.Afterwards by the cooling controlling reaction temperature that exchanges heat at 160 DEG C,
Total time control is reacted at 240 minutes, afterwards blowing, find after blowing, be stained with largely on autoclave body top and blender top
Sticky lump such as water cement.The suspension quantity of slag of discharge is big, cools to 65 DEG C, is filtered with rotary vacuum filter, mistake through heat exchange
1 hour of time to be filtered, a small amount of liquid soluble glass is only obtained by filtration, remaining is not refiltered, and gained liquid is limpid, in dark brown,
There is serious peculiar smell, observe filter cake face last layer black oil ink-like goo, peculiar smell is denseer.
Analyzed through analysis by titration in industrial silicon sodium GB/T4209-2008 standards, the SiO in gained sodium silicate2Content
For 13.61wt%, Na2O content is 5.47wt%, modulus 2.47；Through 722 spectrophotometric analysis, Fe contents therein are
17ppm, Al content 21ppm, heavy metal do not detect.
Comparative example 2：
Its SiO is detected after the high temperature SILICA FUME cooling being directly separated out from smelting industrial silicon flue gas2Content is
94.5wt%, fugitive constituent 3.21wt%, does not roast it, directly with SILICA FUME 24.75Kg, mass concentration 30wt%
Liquid sodium hydroxide 33.5Kg and water 130Kg add belt stirrer 200L reaction kettles in be mixed evenly, be passed directly into
The afterheat steam heating mixed material that pressure is 3.0MPa, temperature is 450 DEG C, controlling reaction temperature is 175 DEG C, pressurize reaction
180 minutes, maximum temperature reached 184 DEG C in reaction kettle after exothermic heat of reaction, reaction generation high temperature waterglass mother liquor.Through changing after discharge
When heat is cooled to 60 DEG C, filtered with rotary vacuum filter, when filtration time 5 is small, obtain isabelline clear liquid waterglass, had obvious
Peculiar smell.One layer of filter cake surface black oil ink-like goo, peculiar smell are dense.
Analyzed through analysis by titration in industrial silicon sodium GB/T4209-2008 standards, the SiO in gained sodium silicate2Content
For 8.82wt%, Na2O content is 2.68wt%, modulus 3.19；Through 722 spectrophotometric analysis, Fe contents therein are
7ppm, Al content 15ppm, heavy metal do not detect；Silica conversion ratio reaches 86.3wt%.
By comparative example, not fired SILICA FUME, the waterglass mass concentration of production is low, it is colored, have peculiar smell, and
Production efficiency is very low, it is difficult to industrializes.And can not only ensure water produced glass quality by the method for the present invention, but also be easy to industrialize
Production.
In conclusion the present invention provides a kind of heat of recycling industrial silicon by-product SILICA FUME and its mineral heating furnace flue
Can, high efficiency, prepare high-purity, high-quality, a kind of brand-new technique and device of different modulus waterglass at low cost, has
Good application prospect.
The invention is not limited in foregoing embodiment.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (10)
- A kind of 1. method using industrial silicon by-product SILICA FUME and waste heat production waterglass, it is characterised in that the described method includes Following steps：The high temperature SILICA FUME that thermal release is collected from smelting industrial silicon flue gas is carried out to the high-temperature roasting under oxygen-enriched atmosphere A, Obtain roasting SILICA FUME；B, the roasting SILICA FUME is added in reaction kettle together with liquid sodium hydroxide/liquid potassium hydroxide and water and be stirred Obtain uniformly and using smelting industrial silicon flue gas as heat source response high temperature waterglass mother liquor；C, the high temperature waterglass mother liquor cooled and filtered is obtained into high-purity waterglass.
- 2. the method for industrial silicon by-product SILICA FUME and waste heat production waterglass is utilized according to claim 1, it is characterised in that In step, using cyclone separator, thermal release collects to obtain high temperature SILICA FUME from smelting industrial silicon flue gas, and the high temperature is micro- The temperature of silica flour is 560~650 DEG C；It is 720~1100 DEG C to control calcination temperature, and roasting time is 15~90 minutes；The roasting Burn non-volatile part in SILICA FUME.
- 3. the method for industrial silicon by-product SILICA FUME and waste heat production waterglass is utilized according to claim 1, it is characterised in that In stepb, SiO is controlled2:NaOH/KOH:H2The mass ratio of O is 2~2.7:1:3~9.5；Controlling reaction temperature for 165~ 210 DEG C, be preferably 170~200 DEG C, more preferably 175~190 DEG C；It is 60~360 minutes to control the reaction time, is preferably 120 ~300 minutes, more preferably 180~240 minutes.
- 4. the method for industrial silicon by-product SILICA FUME and waste heat production waterglass is utilized according to claim 1, it is characterised in that In stepb, be passed through into reaction kettle afterheat steam heating mixed material reacted, wherein, in waste heat boiler by water with The recycling waste heat of the high-temperature flue gas heat exchange after SILICA FUME is isolated from smelting industrial silicon flue gas and obtains the afterheat steam, it is remaining The pressure of hot steam is 1~3MPa, temperature is 220~450 DEG C.
- 5. the method for industrial silicon by-product SILICA FUME and waste heat production waterglass is utilized according to claim 1, it is characterised in that In step C, the high temperature waterglass mother liquor is cooled to room temperature~80 DEG C using pipe heat exchanger, preferably it is cooled to 40~ 80 DEG C, more preferably it is cooled to 50~60 DEG C；Waterglass mother liquor is carried out using rotary vacuum filter or filter press high purity water is obtained by filtration Glass.
- 6. the method for industrial silicon by-product SILICA FUME and waste heat production waterglass is utilized according to claim 1, it is characterised in that The method is further included carries out the recycling of dedusting again and by portion by obtained low-temperature flue gas after high-temperature flue gas recycling waste heat Point afterheat steam again recovery waste heat the step of, wherein, low-temperature flue gas progress dedusting is recycled to obtain fine silicon powder and conjunction Fine silicon powder return is simultaneously carried out high-temperature roasting by lattice tail gas together with high temperature silicon powder, and part of waste heat steam is used to generate electricity And gained electric energy is used to roast high temperature silicon powder.
- 7. the method for industrial silicon by-product SILICA FUME and waste heat production waterglass is utilized according to claim 1, it is characterised in that It is high-purity waterglass water white transparency, tasteless；When high-purity waterglass is sodium silicate, mass concentration in more than 20.0wt%, For dioxide-containing silica in more than 15.5wt%, iron content is less than 10ppm, and aluminium content is less than 25ppm, and content of beary metal is less than 3ppm, modulus are 3~3.4；When high-purity waterglass is potassium water glass, mass concentration contains in more than 22.5wt%, silica Amount is in more than 15.5wt%, and iron content is less than 10ppm, and aluminium content is less than 25ppm, and content of beary metal is less than 3ppm, modulus 3.4 ~3.8.
- 8. a kind of utilize industrial silicon by-product SILICA FUME and the device of waste heat production waterglass, it is characterised in that using described device And according to the method production that industrial silicon by-product SILICA FUME and waste heat production waterglass are utilized any one of claim 1 to 7 Waterglass, described device include separative element, roasting unit, reaction member, heat exchange cooling unit, filter element and Waste Heat Recovery Unit；The smoke inlet of the separative element is connected with industrial silicon exhaust system, the flue gas of exhanst gas outlet and waste heat recovery unit enters The material inlet of mouth connection, material outlet and roasting unit connects；The material outlet of the roasting unit and the material inlet of reaction member connect；The material outlet of the reaction member is connected with the material inlet for the cooling unit that exchanges heat, thermal source inlet and waste heat recovery unit Steam (vapor) outlet connection；Material inlet connection, cooling water inlet and the water source connection of the material outlet and filter element of the heat exchange cooling unit, The material inlet of hot water outlet and reaction member connects.
- 9. industrial silicon by-product SILICA FUME and the device of waste heat production waterglass are utilized according to claim 8, it is characterised in that The separative element is cyclone separator or bag filter, and the roasting unit is roaster, and the reaction member is reaction Kettle, the heat exchange cooling unit is pipe heat exchanger, and the filter element is rotary vacuum filter or filter press, the waste heat recovery unit For waste heat boiler.
- 10. existed according to claim 8 using industrial silicon by-product SILICA FUME and the device of waste heat production waterglass, its feature In described device further includes recovery unit, and the recovery unit includes off-gas recovery subelement and waste heat recovery subelement；The waste heat recovery subelement is generator, and the steam inlet of the generator and the steam (vapor) outlet of waste heat recovery unit connect Connect and the generator is powered directly to roasting unit；The smoke inlet of the off-gas recovery subelement and exhanst gas outlet connection, exhanst gas outlet and the air of waste heat recovery unit connect The material inlet of logical, material outlet and roasting unit connects, and the off-gas recovery subelement includes sequentially connected cloth bag depositing dust Device and desulphurization denitration device.
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