CN102424394B - Process for preparing water glass from silicon micropowder by using wet method - Google Patents
Process for preparing water glass from silicon micropowder by using wet method Download PDFInfo
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- CN102424394B CN102424394B CN 201110268556 CN201110268556A CN102424394B CN 102424394 B CN102424394 B CN 102424394B CN 201110268556 CN201110268556 CN 201110268556 CN 201110268556 A CN201110268556 A CN 201110268556A CN 102424394 B CN102424394 B CN 102424394B
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- water glass
- silica fume
- sio
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Abstract
The invention provides a process for preparing water glass from silicon micropowder by using the wet method, belonging to the technical field of production of water glass. The process comprises the following steps: analyzing the content of SiO2 in silicon micropowder; mixing silicon micropowder and liquid alkali according to a mol ratio of 0.9-1.8:1; delivering obtained mixed liquor into a liquid phase reaction vessel under agitation; allowing steam to enter into the reaction vessel to heat the mixed liquor; carrying out a dwell reaction at a temperature of 70 to 220 DEG C for 0.5 to 6 h so as to prepare mixed liquor of water glass; discharging the mixed liquor of water glass out from the reaction vessel; adjusting the temperature of the mixed liquor of water glass to 50 to 95 DEG C in a feed liquid buffer tank; carrying out plate and frame pressurized filtering to obtain a filtrate which is water glass with a modulus of 1.80 to 3.20. The invention has the following advantages: since the water glass is prepared by using dust in the ferrosilicon alloy industry as a raw material and employing the characteristic that the reaction between amorphous SiO2 in silicon micropowder and alkali liquid has high activity, high conversion efficiency is obtained, the process is simple, the problem of dust pollution in the ferrosilicon alloy industry is overcome, and good economic benefits and social benefits are achieved.
Description
Technical field
The invention belongs to the water glass production technical field.Be particularly related to a kind of method of utilizing the SILICA FUME wet method to prepare water glass.
Background technology
SILICA FUME is in ferro-silicon and industrial silicon production process, the siliceous industrial dust that the SiO that produces in ore-smelting furnace and Si gas are formed by the rapid oxidation of air and condensation.SILICA FUME belongs to pellet (PM10), and the SILICA FUME rear lung that directly enters that is absorbed by the body is very harmful to the person.In recent years, along with the reinforcement of country to the environmental protection dynamics, the environmental protection dust removal installation is installed by cogent provision ferro-silicon and industrial silicon production enterprise, and the SILICA FUME output that ferro-silicon enterprise reclaims constantly increases.
SiO
2Content is used for concrete material between 88～92% SILICA FUME, has good erosion resistance, insulativity, wear resistance, impervious anti-freezing property; SiO
2Content is greater than 92% packing material that can be used as the organic compound such as refractory materials, rubber, resin; And work as SiO
2The SILICA FUME of content lower than 88% time almost do not have market.At present, the application of domestic SILICA FUME is very limited.Patent CN201010170951.5 discloses a kind of active silica fume as the application of rubber, engineering plastic additive white carbon black; But due to the impact of colourity and impurity, SILICA FUME has significant limitation in the use of rubber, engineering plastics.Patent CN200810115333.3 also discloses a kind of method for preparing the titanium white material with SILICA FUME, by being prepared into the titanium dioxide composite material with nucleocapsid structure feature at its surperficial cladding titanium dioxide after SILICA FUME activation, removal of impurities, dispersion, adjustment sheet surface charge; But this processing method is complicated, the TiO of surface coating layer in composite particles
2Structure be difficult to control.
SiO in SILICA FUME
2Have typical non-crystalline state feature, content generally can reach 69.3% (wt)～93.5% (wt).Amorphous Si O
2The more, SILICA FUME is active larger, and response capacity is stronger in basic solution.Therefore, preparing soluble glass of high modulus take SILICA FUME as raw material is ferro-silicon industrial dust higher value application and the effective ways that reduce the dust secondary pollution.
Water glass is a kind of purposes inorganic chemical product very widely.The production method of water glass is divided into two kinds of dry method and wet methods, wherein dry method be with quartz sand and sodium carbonate or sodium sulfate 1400～1500 ℃ melt stove in the frit reaction preparation.Be characterized in to prepare as required the water glass product of different moduluses, but power consumption is larger.Wet method is to be 140～160 ℃ with sodium hydroxide solution and quartz sand in temperature, and pressure is that under 0.37～0.63MPa condition, reaction is produced.Although energy consumption is lower than dry method, crystal habit SiO in quartz sand
2Dissolution rate is low, alkaline consumption is high.
For taking full advantage of resource, reducing production costs, many researchs just are being devoted to develop the new technology of different silicon source production water glass.Patent CN201010176401.4 discloses a kind of with rice hull ash and sodium carbonate mixing, the method for burning solid water glass at the temperature of 900 ℃; Patent CN200910072958.0 also discloses and has a kind ofly utilized rice hull ash and alkali reaction after power plant burning to generate sodium silicate solution or colloidal sol, and insolubles makes the method for activated carbon product through acidification; Patent CN200810132277.4 discloses a kind of with the active silica in white liquor leaching industrial flyash, dissolves the method for the sodium silicate solution of preparation high-module by silicic acid and low modulus water glass; Patent CN200610017165.5 discloses and a kind of coal gangue has been generated alum liquor with the sulfuric acid reaction of concentration 40～60% in reactor, and the silicon-dioxide filter residue reacts with liquid caustic soda the method that makes liquid sodium silicate.CN200410058137.9 also discloses a kind of take coal series kaolin rock as main raw material, by acidleach, and the method for the molten production polymerize aluminum chloride of sour molten slag alkali and high-module liquid sodium silicate; Patent CN200910154795.0 discloses a kind of aluminium scrap ash and Na of utilizing
2CO
3The method for preparing crystal aluminum chloride and water glass by the high temperature solid-state thermolysis; Patent CN201010230406.0 discloses a kind of method of utilizing organosilicon or polysilicon industry preparing water glass from byproduct silicon tetrachloride; Patent CN200910102418.2 discloses a kind of silica containing fluorine of Phosphate Fertilizer Industry by-product that utilizes and has prepared the method for water glass for raw material; Patent CN200580051917.3 also discloses a kind of method that kimberlite ore deposit for producing as solid waste from diamond mining prepares water glass.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing the SILICA FUME wet method to prepare water glass.Solved the large technology barrier of dissolving with higher value application of ferro-silicon industrial dust, for the higher value application of ferro-silicon or Pure Silicon Metal manufacture dust provides simple and effective new way.
In order to solve the problems of the technologies described above, concrete technological step is as follows:
1, analyze SiO in the supplied materials SILICA FUME
2Content
SILICA FUME is that silicon is the flue dust that iron alloy (as Pure Silicon Metal, ferro-silicon, silicomanganese etc.) industrial furnace produces, the siliceous dust of collecting by cleaning apparatus.SiO wherein
2: the SILICA FUME of 69.3～93.5% (wt) can be used as raw material.Other chemical compositions have following scope: Al
2O
3: 0.35～0.38% (wt); Fe
2O
3: 0.40～4.80% (wt); CaO:0.17～1.20% (wt); MgO:0.4～5.19% (wt); C:0.46～0.52% (wt); K
2O:1.01～7.97% (wt); Na
2O:0.22～1.52% (wt); Loss on ignition: 2.18～4.61% (wt).
To meet SiO
2: 69.3～93.5% (wt), preferable range is that the SILICA FUME of 83～93.5% (wt) is made raw material, the alkali lye that is 30-50% (wt) with SILICA FUME and naoh concentration mixes mutually, wherein SiO
2: the NaOH mol ratio is controlled to be 0.90～1.80: 1, and preferable range is 1.20～1.60: 1.
2, will go on foot poly-1 mixed solution that makes with being pumped in the liquid phase reaction still of opening stirring under whipped state, pass into the water vapor direct heating in reactor.Reactor temperature is controlled at 70～220 ℃, and preferable range is 152～170 ℃, reacts to make the water glass mixed solution after 0.5～6 hour.
3, step 2 gained water glass mixed solution is discharged reactor, enter in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 50～95 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, it is 1.80～3.20 water glass that gained filtrate is modulus.
The invention has the advantages that:
Take the industrial SILICA FUME of collecting of ferro-silicon as raw material, take full advantage of amorphous Si O in SILICA FUME
2Prepare water glass with the active high characteristics of alkaline reaction, technical process is simple, workable, has solved the large technology barrier of dissolving with higher value application of ferro-silicon industrial dust.Be the recycling SILICA FUME, high-level efficiency, the high-quality water glass of low-cost preparation provide a new approach.
Embodiment
Embodiment 1:
1, take SILICA FUME 120kg and be placed in dosing vessel, analyze to get SiO
2Content is 83.3% (wt).Adding naoh concentration is 50% (wt) alkali lye, with mixed solution SiO
2: the NaOH mol ratio is modulated into 1.30: 1.
2, the mixed solution that under whipped state, step 1 is made passes into the water vapor direct heating with being pumped in the liquid phase reaction still of opening stirring in reactor.When reaching 0.6MPa, the still internal pressure stops steam supply; The still internal pressure keeps 0.6MPa, and temperature is controlled to be 158 ℃, and the pressurize reaction made the water glass mixed solution in 3 hours.
3, reactor is depressurized to 0.3MPa, and step 2 gained water glass mixed solution is discharged reactor by overbottom pressure, enters in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 90 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, gained filtrate is water glass.Through the silicon molybdenum blue spectrophotometric analysis, SiO in water glass
2Content is 9.30% (wt), and modulus is 2.50, SiO in SILICA FUME
2Transformation efficiency be 78.3%.
Embodiment 2:
1, take SILICA FUME 160kg and be placed in dosing vessel, analyze to get SiO
2Content is 78.2% (wt).Adding naoh concentration is 50% (wt) alkali lye, with mixed solution SiO
2: the NaOH mol ratio is modulated into 1.80: 1.
2, the mixed solution that under whipped state, step 1 is made passes into the water vapor direct heating with being pumped in the liquid phase reaction still of opening stirring in reactor.The control temperature in the kettle reaches 70 ℃, reacts to make the water glass mixed solution in 6 hours.
3, step 2 gained water glass mixed solution is discharged reactor, enter in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 50 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, gained filtrate is water glass.Through the silicon molybdenum blue spectrophotometric analysis, SiO in water glass
2Content is 8.60% (wt), and modulus is 3.2, SiO in SILICA FUME
2Transformation efficiency be 67.4%.
Embodiment 3:
1, take SILICA FUME 160kg and be placed in dosing vessel, analyze to get SiO
2Content is 92.2% (wt).Adding naoh concentration is 30% (wt) alkali lye, with mixed solution SiO
2: the NaOH mol ratio is modulated into 1.40: 1.
2, the mixed solution that under whipped state, step 1 is made passes into the water vapor direct heating with being pumped in the liquid phase reaction still of opening stirring in reactor.When reaching 0.8MPa, the still internal pressure stops steam supply; The still internal pressure keeps 0.8MPa, and temperature is controlled to be 170 ℃, and the pressurize reaction made the water glass mixed solution in 3 hours.
3, reactor is depressurized to 0.15MPa, and step 2 gained water glass mixed solution is discharged reactor by overbottom pressure, enters in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 80 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, gained filtrate is water glass.Through the silicon molybdenum blue spectrophotometric analysis, SiO in water glass
2Content is 12.80% (wt), and modulus is 2.7, SiO in SILICA FUME
2Transformation efficiency be 84.6%.
Embodiment 4:
1, take SILICA FUME 120kg and be placed in dosing vessel, analyze to get SiO
2Content is 83.3% (wt).Adding naoh concentration is 40% (wt) alkali lye, with mixed solution SiO
2: the NaOH mol ratio is modulated into 1.60: 1.
2, the mixed solution that under whipped state, step 1 is made passes into the water vapor direct heating with being pumped in the liquid phase reaction still of opening stirring in reactor.When reaching 0.6MPa, the still internal pressure stops steam supply; The still internal pressure keeps 0.6MPa, and temperature is controlled to be 158 ℃, and the pressurize reaction made the water glass mixed solution in 0.5 hour.
3, reactor is depressurized to 0.20MPa, and step 2 gained water glass mixed solution is discharged reactor by overbottom pressure, enters in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 80 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, gained filtrate is water glass.Through the silicon molybdenum blue spectrophotometric analysis, SiO in water glass
2Content is 11.60% (wt), and modulus is 3.1, SiO in SILICA FUME
2Transformation efficiency be 80.4%.
Embodiment 5:
1, take SILICA FUME 120kg and be placed in dosing vessel, analyze to get SiO
2Content is 92.2% (wt).Adding naoh concentration is 40% (wt) alkali lye, with mixed solution SiO
2: the NaOH mol ratio is modulated into 0.95: 1.Mixed solution passes into water vapor direct heating to 90 ℃.
2, the mixed solution that under whipped state, step 1 is made passes into the water vapor direct heating with being pumped in the liquid phase reaction still of opening stirring in reactor.When reaching 0.8MPa, the still internal pressure stops steam supply.The still internal pressure keeps 0.8MPa, and temperature is controlled to be 170 ℃, and the pressurize reaction made the water glass mixed solution in 1 hour.
3, reactor is depressurized to 0.25MPa, and step 2 gained water glass mixed solution is discharged reactor by overbottom pressure, enters in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 50 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, gained filtrate is water glass.Through the silicon molybdenum blue spectrophotometric analysis, SiO in water glass
2Content is 5.60% (wt), and modulus is 1.82, SiO in SILICA FUME
2Transformation efficiency be 90.9%.
Embodiment 6:
1, take SILICA FUME 120kg and be placed in dosing vessel, analyze to get SiO
2Content is 92.2% (wt).Adding naoh concentration is 40% (wt) alkali lye, with mixed solution SiO
2: the NaOH mol ratio is modulated into 1.30: 1.Mixed solution passes into water vapor direct heating to 70 ℃.
2, the mixed solution that under whipped state, step 1 is made passes into the water vapor direct heating with being pumped in the liquid phase reaction still of opening stirring in reactor.When reaching 2.4Mpa, the still internal pressure stops steam supply; The still internal pressure keeps 2.5MPa, and temperature is controlled to be 220 ℃, and the pressurize reaction made the water glass mixed solution in 3 hours.
3, reactor is depressurized to 0.3MPa, and step 2 gained water glass mixed solution is discharged reactor by overbottom pressure, enters in the feed liquid surge tank.Add water and regulate water glass mixeding liquid temperature to 90 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, gained filtrate is water glass.Through the silicon molybdenum blue spectrophotometric analysis, SiO in water glass
2Content is 12.20% (wt), and modulus is 2.50, SiO in SILICA FUME
2Transformation efficiency be 94.3%.
Claims (4)
1. a method of utilizing the SILICA FUME wet method to prepare water glass, is characterized in that, processing step is:
(1) analyze SiO in the SILICA FUME raw material
2Content, will meet SiO
2: the SILICA FUME of 69.3～93.5wt% is made raw material, and the alkali lye that is 30-50 wt % with SILICA FUME and naoh concentration mixes mutually, wherein SiO
2: the NaOH mol ratio is controlled to be 0.90～1.80:1;
(2) will go on foot mixed solution that poly-(1) make with being pumped in the liquid phase reaction still of opening stirring under whipped state, pass into the water vapor direct heating in reactor, make the water glass mixed solution in pressurize reaction under 70～220 ℃ of conditions of temperature after 0.5～6 hour;
(3) step (2) gained water glass mixed solution is discharged reactor, enter in the feed liquid surge tank, add water and regulate water glass mixeding liquid temperature to 50～95 ℃ in the feed liquid surge tank, through sheet frame pressure filtration, it is 1.80～3.20 water glass that gained filtrate namely gets modulus;
Described SILICA FUME is that silicon is the flue dust that the ferroalloy industry electric furnace produces, the siliceous dust of collecting by cleaning apparatus.
2. method according to claim 1, is characterized in that, SiO
2Content is 83～93.5 wt %.
3. method according to claim 1, is characterized in that, SiO in step (1) SILICA FUME and alkali lye premix
2: the NaOH mol ratio is 1.20～1.60:1.
4. method according to claim 1, is characterized in that, in step (2), the reactor temperature span of control is 152～170 ℃.
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| BR102020016451B1 (en) * | 2020-08-12 | 2021-11-03 | Pq Silicas Brazil Ltda | STABLE SODIUM AND IRON SILICATE SOLUTION PROCESS TO PREPARE SUCH SOLUTION AND ITS USES |
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| JPS5727922A (en) * | 1980-07-25 | 1982-02-15 | Shokubai Kasei Kogyo Kk | Wet manufacture of sodium silicate |
| DE3938729A1 (en) * | 1989-11-23 | 1991-05-29 | Henkel Kgaa | METHOD FOR THE HYDROTHERMAL PRODUCTION OF SODIUM POLYSILICATE |
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