CN102190310A - Method for manufacturing sodium metasilicate nonahydrate with fly ashes - Google Patents
Method for manufacturing sodium metasilicate nonahydrate with fly ashes Download PDFInfo
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- CN102190310A CN102190310A CN 201110120102 CN201110120102A CN102190310A CN 102190310 A CN102190310 A CN 102190310A CN 201110120102 CN201110120102 CN 201110120102 CN 201110120102 A CN201110120102 A CN 201110120102A CN 102190310 A CN102190310 A CN 102190310A
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- desiliconization
- liquid
- flyash
- sodium metasilicate
- solid
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- 239000010881 fly ash Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 93
- 239000007788 liquid Substances 0.000 claims abstract description 75
- 239000013078 crystal Substances 0.000 claims abstract description 51
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 53
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 53
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 47
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 claims description 45
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 23
- 238000001704 evaporation Methods 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 230000008719 thickening Effects 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 235000011121 sodium hydroxide Nutrition 0.000 description 29
- 238000002425 crystallisation Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 18
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 17
- 239000003513 alkali Substances 0.000 description 14
- 235000019353 potassium silicate Nutrition 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 238000009413 insulation Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 11
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000007605 air drying Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011549 crystallization solution Substances 0.000 description 4
- 239000011268 mixed slurry Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010017472 Fumbling Diseases 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
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- 239000012452 mother liquor Substances 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
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Images
Abstract
The invention discloses a method for manufacturing sodium metasilicate nonahydrate with fly ashes, comprising the steps of: adding fly ashes into a sodium hydroxide solution for desilication, then performing a solid-liquid separation, thus obtaining a first desiliconized liquid; adding fly ashes into the first desiliconized liquid for a second desilication, then performing a solid-liquid separation, thus obtaining a second desiliconized liquid; evaporating and thickening the second desiliconized liquid, and when the content of SiO2 accounts for 120-150g/L, stopping evaporating and thickening and starting cooling, then adding sodium metasilicate nonahydrate crystals into the second desiliconized liquid as a seed crystal, then precipitating crystals; performing a solid-liquid separation to the second desiliconized liquid from which the crystals are precipitated, so that a solid product can be obtained, then drying the solid product so as to obtain the product of sodium metasilicate nonahydrate. Adoption of the method provided in the invention overcomes lots of disadvantages of the prior art, and enjoys the advantages of easily available raw material, low cost, good product quality, improved production efficiency as well as easy industrialization promotion.
Description
Technical field
The present invention relates to a kind of recycling of flyash, relate in particular to a kind of method of utilizing flyash to produce non-hydrate sodium metasilicate.
Background technology
Non-hydrate sodium metasilicate is the white crystals sprills, relative density 0.7～0.9,40～48 ℃ of fusing points.Soluble in water and dilute alkaline soln is insoluble to pure and mild acid, and the aqueous solution is alkalescence, is placed in the air easily moisture absorption deliquescence.Non-hydrate sodium metasilicate mainly serves as the high effective additives in washing powder, metal cleaner, the dishwashing detergent, also is applied to cotton yarn boiling, old paper removal ink, printing decontamination, vegetables oil recovery, and can be used as the stablizer of peroxide bleaching.In addition, non-hydrate sodium metasilicate has a large amount of application at industrial circles such as washing composition, pottery, plating, weaving, printing and dyeing, papermaking, cement, concrete, refractory materials, grease and leather processing.
The synthetic method of traditional Starso has spray-drying process, blow knot time comminution granulation and solution crystal process.Wherein, solution crystal process technology has that facility investment is few, production cost is low, stay-in-grade characteristics.The conventional processes of non-hydrate sodium metasilicate solution crystal process is as follows: common bubble flower alkali and caustic soda are dissolved under high temperature, high pressure, pass through hydro-thermal reaction, bubble flower alkali and caustic soda are fully reacted, through crystallization, separation, the wet cake drying obtains low molecular weight smectic body product, and isolating mother liquor is treated to be returned technical process and recycle.The production of non-hydrate sodium metasilicate generally comprises: reaction → crystallization → three processes of filtration, wherein crystallization is the key link in the technology.Traditional crystallization processes method has two classes: a kind of is that solution evaporation is arrived supersaturation and crystallization, and another kind is to make the solution cooling reach supersaturation and crystallization.
Flyash is the main waste of firepower electrical plant, and its quantity discharged increases year by year, because of it occupies a large amount of soils, an influence storage ash ambient air quality and agriculture production, thus the serious harm environment.Present stage utilizes flyash to produce white carbon black, the aluminum oxide road that moves towards the industrialization gradually, and utilize flyash to produce the stage of fumbling that Technology such as non-hydrate sodium metasilicate also is in industry.
Present domestic ordinary method is produced non-hydrate sodium metasilicate and is had following two technical problems:
1, the producer that produces non-hydrate sodium metasilicate both at home and abroad is a raw material to steep colored alkali and caustic soda mostly, and bubble flower base this by ores and soda ash (or native alkali) congruent melting in the fusing kiln such as quartz sands, the cooling pulverizing makes.Thereby the selection of raw material not only has limitation but also consumes a large amount of non-renewable Mineral resources, havoc the eubiosis.
2, to disclose with flyash and sodium hydroxide be raw material production non-hydrate sodium metasilicate or metasilicate pentahydrate sodium to a few studies data, but because of the raw material-desiliconization liquid or the modulus too low (generally being no more than 0.5) of preparation water glass, or desiliconization liquid SiO
2Concentration is too low, prepares qualified water glass product processes complexity by this desiliconization liquid, and energy consumption alkaline consumption height is difficult to Industry Promotion.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing flyash to produce non-hydrate sodium metasilicate, realized that raw material sources are extensive, with low cost, quality product is good, production efficiency improves, be easy to Industry Promotion.
Utilize flyash to produce the method for non-hydrate sodium metasilicate, comprise the steps:
1), flyash is joined desiliconization in the sodium hydroxide solution, carries out solid-liquid separation after the desiliconization, obtain the one-step desilication of liquid phase;
2), get flyash and join and carry out the secondary desiliconization in the described one-step desilication, carry out solid-liquid separation after the desiliconization, obtain the secondary desiliconization liquid of liquid phase;
3), described secondary desiliconization liquid is evaporated enrichment, SiO in the secondary desiliconization liquid
2When content is 120～150g/L, stops to evaporate enrichment and begin cooling, when temperature is 35～45 ℃, in described secondary desiliconization liquid, add non-hydrate sodium metasilicate, stir slowly, promote to separate out crystal as crystal seed;
4), will separate out crystalline secondary desiliconization liquid solid-liquid separation, the solid phase drying with solid-liquid separation obtains obtains the product non-hydrate sodium metasilicate.
Further, described flyash is power plant's solid waste coal ash, wherein SiO
2Weight percentage be 30～50%.
Further, described in the step 1) in the sodium hydroxide solution sodium hydroxide concentration be 12%～18%; The mass ratio of sodium hydroxide and flyash butt is 0.4～0.6: 1; The desiliconization temperature is 110～130 ℃, and desiliconization time is 1～2h.
The mass ratio of one-step desilication step 2 further) and flyash butt is 3 ± 0.5: 1; Secondary desiliconization temperature is 115～135 ℃, and the secondary desiliconization time is 1～2h.
Adopt the secondary desiliconization and do not adopt the major cause that strengthens the flyash metering to be: when Industry Promotion, add a large amount of flyash, will cause following difficulty: 1) desiliconization slurry liquid-solid ratio reduces, solids content increases, cause the solution viscosity to strengthen, the material spread coefficient of slurries is reduced, bring difficulty for the exchange of substance of flyash and alkali lye, thereby cause desiliconization effect to reduce.When carrying out solid-liquid separation, run into the fluctuation of temperature a little simultaneously, a large amount of hydrolysis of water glass just take place easily, the silicon that causes taking off is hydrolyzed into metasilicic acid again, comes back in the flyash and goes, and reduces desiliconization effect equally.2) the high slurries that contain are admittedly all bringing big difficulty aspect slip conveying, filtration and the alkali lye recovery.Adopt the secondary desiliconization, remain on the higher level about 3 can guarantee the liquid-solid ratio of each desiliconization slurries, although the second time desiliconization effect have a little and reduce, but more far better than a high desiliconization effect that contains admittedly.Therefore adopt the secondary desiliconization can avoid occurring above-mentioned two kinds of situations, be suitable for Industry Promotion.
When first time desiliconization, in order to guarantee enough desiliconization effects, it is excessive that sodium hydroxide adds, the modulus of the desiliconization liquid that obtains is generally 0.45～0.5, during desiliconization for the second time, add less water again, guarantee that the liquid-solid ratio of desiliconization slurries maintains about 3 to 1 with primary desiliconization liquid.No longer include replenishing of alkali in the desiliconization this moment system, only contain non-crystalline state SiO
2Flyash replenish, therefore when the secondary desiliconization, have a large amount of SiO
2Enter in the one-step desilication, thereby the modulus of desiliconization liquid can be brought up to about 1.0.After twice desiliconization, the modulus of desiliconization liquid rises to about 1.0 from about 0.5, the proportioning of silicon and sodium meets the production requirement of non-hydrate sodium metasilicate in secondary desiliconization liquid this moment (water glass), and the alkali concn in the desiliconization liquid keeps lower level, can in evaporation enrichment and temperature-fall period, control effectively to alkali concn, the pH that guarantees product meets the requirements, thereby produces qualified product.The modulus testing method of desiliconization liquid is as follows: at first test SiO in the desiliconization liquid
2Concentration, wherein Na of test then
2O
k(severe alkali concn), the mol ratio of the two is exactly the modulus of desiliconization liquid.The modulus of desiliconization liquid mainly is subjected to following controlling factors: the non-crystalline state SiO of flyash
2In content, the desiliconization liquid concentration of NaOH, desiliconization liquid consolidate contain, the desiliconization temperature and time.
Further, weight as the described non-hydrate sodium metasilicate of crystal seed in the step 3) is 5～10% of secondary desiliconization liquid gross weight, adding crystal seed stirs simultaneously slowly, crystal seed is suspended in the secondary desiliconization solution uniformly, wait crystalline material is grown up rapidly at seed surface, thereby promote the crystallization reaction; The temperature-fall period that adds behind the crystal seed was controlled at 3～4 hours: begin that cooling rate is controlled at 3～5 ℃/h in 2 hours, is to lower the temperature naturally afterwards.The present invention has controlled 3 key elements 1 of crystallization process effectively) quality of desiliconization liquid, the i.e. modulus of desiliconization liquid and SiO
2Concentration; 2) control of evaporative process is about to the SiO in the desiliconization liquid
2Concentration is evaporated to 120～150g/L and both can; 3) quality of water glass crystal seed and addition, seed size will suit, and satisfies customer requirements to guarantee the crystallization granularity.Having a large amount of non-hydrate sodium metasilicate crystal in this process separates out.
Further, solid-liquid separation adopts spin-on filter device to finish in the step 4), and the desiliconization liquid after the solid-liquid separation adds sodium hydroxide again and recycles, and is about to it and is mixed with desiliconization dope repeating step 1) and step 2).The non-hydrate sodium metasilicate that centrifugation obtains moisture 3～4%, with the crystal seed of non-hydrate sodium metasilicate as secondary desiliconization liquid crystallization, this part crystal drying-free directly continues to recycle, all the other crystal then place the baking oven forced air drying about 35 ℃, 2～3 hours time of drying, after finishing, drying obtains the product non-hydrate sodium metasilicate.The method that the sodium silicate solution that this processing method obtains matches by evaporation enrichment and cooling crystallization, under the condition that adds crystal seed, the time of crystallization shortens significantly, the crystallisation process of traditional technology approximately needs 5～7 hours, we's rule was reduced to 3～4 hours, therefore improve production efficiency, made interior single pot of productive rate of unit time increase about 15%.
Further, step 1) and step 2) in the liquid-solid solid phase that obtains of separating be desiliconization slag, the alumina silica ratio of described desiliconization slag is 1.5～2.5, and described desiliconization slag can make like this that for producing the raw material of aluminum oxide or refractory materials main component silicon oxide and the aluminum oxide in the flyash is fully used.
The present invention utilizes the methodological science of flyash production non-hydrate sodium metasilicate reasonable, with flyash is raw material, adopt the finite concentration sodium hydroxide solution successively two batches of flyash to be carried out desiliconization and obtain the sodium silicate solution of finite concentration and modulus, then this sodium silicate solution is evaporated enrichment, and the adding crystal seed carries out crystallization in cooling, will separate out to obtain the product non-hydrate sodium metasilicate after crystal separation is also handled.Compare with existing non-hydrate sodium metasilicate production technology, mainly have with several respects advantage:
(1) use non-renewable Mineral resources different as initial feed with traditional technology, raw material of the present invention is a waste flyash, and wide material sources, with low cost have effectively been protected the eubiosis.
(2) owing to adopt twice desiliconization method that flyash is carried out pre-desiliconization, the modulus of secondary desiliconization liquid mesosilicic acid sodium is brought up near 1.0, with water glass composition basically identical, and SiO
2Concentration is up to 100g/l.Prepare non-hydrate sodium metasilicate by this desiliconization liquid, can obviously cut down the consumption of energy.The related temperature and pressure of its production process is all lower in addition, and is also relatively low to equipment requirements, so the present invention is easy to Industry Promotion.
Description of drawings
Accompanying drawing is used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used from explanation the present invention with embodiments of the invention one, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is technological process of production figure of the present invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
Present method is a raw material with industrial waste resource flyash, adopt the finite concentration sodium hydroxide solution successively two batches of flyash to be carried out desiliconization and obtain the sodium silicate solution (qualified water glass) of finite concentration and modulus, in enrichment evaporation and decrease temperature crystalline, add crystal seed and quicken the crystallization process, crystal separation and processing with separating out finally obtain the product non-hydrate sodium metasilicate.The crystallization method that this process using evaporation enrichment and cooling cooling combine can effectively be enhanced productivity.The reactions steps, conditional request and the detection method that are prepared non-hydrate sodium metasilicate by above method further specify in conjunction with specific embodiments.
Embodiment 1:
Fig. 1 is technological process of production figure of the present invention.As shown in Figure 1, the disclosed method of utilizing flyash to produce non-hydrate sodium metasilicate of present embodiment comprises the steps:
1) 15gNaOH is dissolved in the 85ml water and is warming up to 120 ℃ and dispose sodium hydroxide solutions, getting 30g flyash slowly joins in the sodium hydroxide solution, stir while adding, after flyash and alkali lye mix, insulation reaction 1.5h, then dope filtration is separated, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is one-step desilication.
2) one-step desilication is warming up to 125 ℃, gets flyash 35g again and slowly put in the middle of the one-step desilication, the limit edged stirs, after mixing, insulation reaction 1.5h separates dope filtration then, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is the secondary desiliconization liquid.
3) enrichment is evaporated in the insulation under 101 ℃ of this desiliconization liquid, to SiO
2Content is that 140g/L, modulus are about 1 to begin to cool to 40 ℃, add 5g non-hydrate sodium metasilicate crystal as crystal seed thereafter, add fashionable slow stirring, crystal seed is suspended in the whole solution uniformly, and crystallization solution slowly is cooled to room temperature in 4h, during have a large amount of crystal from solution, to separate out.
4) mixed slurry is separated with centrifugal filter, solids constituent from after desiliconization liquid add sodium hydroxide again and recycle, be about to it and be mixed with desiliconization dope repeating step 1) and step 2).The solid sub-fraction that obtains is used as crystal seed, and all the other are placed into forced air drying in 35 ℃ the baking oven, and drying time is 2h, and the crystal after the oven dry is exactly the product non-hydrate sodium metasilicate.
The present invention carries out the secondary desiliconization by sig water to flyash, and main purpose is the modulus (SiO with desiliconization liquid
2/ Na
2The O mol ratio) brings up near 1.0 by original about 0.5, and improve the SiO of desiliconization liquid
2Concentration, and then further improve SiO in the desiliconization liquid by means such as evaporation enrichment and coolings
2Concentration and the degree of supersaturation of water glass, thereby can increase crystallization speed, shorten crystallization time.And the pH that can guarantee product meets the requirements.As only adopting 15% NaOH solution that flyash is carried out sodium silicate solution (desiliconization liquid) SiO that a time desiliconization obtained
2Concentration only is 50～60g/l, and modulus only is 0.45～0.5, by this desiliconization liquid carry out direct concentration and evaporation, the cooling crystallization prepare non-hydrate sodium metasilicate, its energy consumption is higher, and be mingled with a large amount of free NaOHs in the product that is obtained and be difficult to wash off, so the pH of product is difficult to meet the requirements.But under the prerequisite of grasping desiliconization temperature, liquid-solid desiliconization time when, utilize one-step desilication that next batch flyash is carried out the secondary desiliconization, the secondary sodium silicate solution SiO that is obtained
2Concentration will be brought up to 90～100g/l, and modulus can bring up to 0.95～1.0, prepares non-hydrate sodium metasilicate by this desiliconization liquid, and the evaporation energy consumption will obviously reduce, and because SiO in the desiliconization liquid
2/ Na
2O meets the composition requirement of nine water water glass, so the most Na in the desiliconization liquid
2O will be with the form crystallization of non-hydrate sodium metasilicate, and wherein being mingled with the NaOH amount can obviously reduce, and wash off than being easier to, so the pH of product can meet the requirements.According to the testing method of powder pH value standard, it is 1% the aqueous solution that the nine water water glass that present embodiment obtained are prepared into mass concentration, and shown pH value (the pH value of product just) is 12.3.
Embodiment 2:
The disclosed method of utilizing flyash to produce non-hydrate sodium metasilicate of present embodiment comprises the steps:
1) 12gNaOH is dissolved in the 88ml water and is warming up to 110 ℃, getting 20g flyash more slowly joins in the sodium hydroxide solution, the limit edged stirs, after flyash and alkali lye mix, insulation reaction 2h, then dope filtration is separated, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is one-step desilication.
2) one-step desilication is warming up to 115 ℃, gets flyash 30g again and slowly put in the middle of the one-step desilication, the limit edged stirs, after mixing, insulation reaction 2h separates dope filtration then, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is the secondary desiliconization liquid.
3) enrichment is evaporated in the insulation under 101 ℃ of secondary desiliconization liquid, to SiO
2Content is that 150g/L, modulus are about 1 to begin to cool to 45 ℃, add 4g non-hydrate sodium metasilicate crystal as crystal seed thereafter, add fashionable slow stirring, crystal seed is suspended in the whole solution uniformly, and crystallization solution slowly is cooled to room temperature in 3h, during have a large amount of crystal and from solution, separate out.
4) mixed slurry is separated with centrifugal filter, the desiliconization liquid after the separation adds sodium hydroxide again and recycles, and is about to it and is mixed with desiliconization dope repeating step 1) and step 2).The solid sub-fraction that obtains is used as crystal seed, and all the other are placed into forced air drying in 35 ℃ the baking oven, and drying time is 2h, and the crystal after the oven dry is exactly the product non-hydrate sodium metasilicate.It is 1% the aqueous solution that the nine water water glass that present embodiment obtained are prepared into mass concentration, and shown pH value (the pH value of product just) is 11.5.
Embodiment 3:
The disclosed method of utilizing flyash to produce non-hydrate sodium metasilicate of present embodiment comprises the steps:
1) 18gNaOH is dissolved in the 82ml water and is warming up to 130 ℃, getting 40g flyash more slowly joins in the middle of the alkaline solution, stir while adding, after flyash and alkali lye mix, insulation reaction 1h, then dope filtration is separated, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is one-step desilication.
2) one-step desilication is warming up to 135 ℃, gets flyash 40g again and slowly put in the middle of the one-step desilication, the limit edged stirs, after mixing, insulation reaction 1h separates dope filtration then, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is the secondary desiliconization liquid.
3) enrichment is evaporated in the insulation under 101 ℃ of secondary desiliconization liquid, to SiO
2Content is that 130g/L, modulus are about 1 to begin to cool to 35 ℃, add 6g non-hydrate sodium metasilicate crystal as crystal seed thereafter, add fashionable slow stirring, crystal seed is suspended in the whole solution uniformly, and crystallization solution slowly is cooled to room temperature in 4h, during have a large amount of crystal and from solution, separate out.
4) mixed slurry is separated with centrifugal filter, the desiliconization liquid after the separation adds sodium hydroxide again and recycles, and is about to it and is mixed with desiliconization dope repeating step 1) and step 2).The solid sub-fraction that obtains is used as crystal seed, and all the other are placed into forced air drying in 35 ℃ the baking oven, and drying time is 2.5h, and the crystal after the oven dry is exactly the product non-hydrate sodium metasilicate.It is 1% the aqueous solution that the nine water water glass that present embodiment obtained are prepared into mass concentration, and shown pH value (the pH value of product just) is 11.6.
Embodiment 4:
The disclosed method of utilizing flyash to produce non-hydrate sodium metasilicate of present embodiment comprises the steps:
1) 16gNaOH is dissolved in the 84ml water and is warming up to 125 ℃, getting 36g flyash more slowly joins in the middle of the alkaline solution, stir while adding, after flyash and alkali lye mix, insulation reaction 1.5h, then dope filtration is separated, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is one-step desilication.
2) it is warming up to 130 ℃, gets flyash 40g again and slowly put in the middle of the one-step desilication, the limit edged stirs, after mixing, insulation reaction 1.5h separates dope filtration then, gained solid desiliconization slag is used to produce aluminum oxide, and the filtrate that obtains is the secondary desiliconization liquid.
3) enrichment is evaporated in the insulation under 101 ℃ of secondary desiliconization liquid, to SiO
2Content is that 150g/L, modulus are about 1 to begin to cool to 42 ℃, add 5g non-hydrate sodium metasilicate crystal as crystal seed thereafter, add fashionable slow stirring, crystal seed is suspended in the whole solution uniformly, and crystallization solution slowly is cooled to room temperature in 3.5h, during have a large amount of crystal and from solution, separate out.
4) mixed slurry is separated with centrifugal filter, the desiliconization liquid after the separation adds sodium hydroxide again and recycles, and is about to it and is mixed with desiliconization dope repeating step 1) and step 2).The solid sub-fraction that obtains is used as crystal seed, and all the other are placed into forced air drying in 35 ℃ the baking oven, and drying time is 3h, and the crystal after the oven dry is exactly the product non-hydrate sodium metasilicate.It is 1% the aqueous solution that the nine water water glass that present embodiment obtained are prepared into mass concentration, and shown pH value (the pH value of product just) is 10.8.
The present invention is not limited only to above-mentioned four groups of described technical schemes of embodiment, as long as adopted secondary or twice above desiliconization, further improves SiO in the desiliconization liquid by means such as evaporation enrichment and coolings again
2The concentration and the degree of supersaturation of water glass all should be in protection scope of the present invention.
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a method of utilizing flyash to produce non-hydrate sodium metasilicate is characterized in that, comprises the steps:
1), flyash is joined desiliconization in the sodium hydroxide solution, carries out the one-step desilication that solid-liquid separation obtains liquid phase after the desiliconization;
2), get flyash and join and carry out the secondary desiliconization in the described one-step desilication, carry out the secondary desiliconization liquid that solid-liquid separation obtains liquid phase after the secondary desiliconization;
3), described secondary desiliconization liquid is evaporated enrichment, SiO in the secondary desiliconization liquid
2When content is 120～150g/L, stops to evaporate enrichment and begin cooling; When temperature drops to 35～45 ℃, in described secondary desiliconization liquid, add non-hydrate sodium metasilicate as crystal seed, separate out crystal;
4), will separate out crystalline secondary desiliconization liquid solid-liquid separation and obtain solid product, obtain non-hydrate sodium metasilicate after the solid product drying.
2. method according to claim 1 is characterized in that, SiO in the described flyash
2Weight percentage be 30～50%.
3. method according to claim 1 is characterized in that, sodium hydroxide concentration is 12%～18% in the described sodium hydroxide solution of step 1); The mass ratio of sodium hydroxide and flyash butt is 0.4～0.6: 1.
4. method according to claim 1 is characterized in that, the described desiliconization temperature of step 1) is 110～130 ℃, and desiliconization time is 1～2h.
5. method according to claim 1 is characterized in that step 2) mass ratio of described one-step desilication and flyash butt is 3 ± 0.5: 1.
6. method according to claim 1 is characterized in that step 2) described secondary desiliconization temperature is 115～135 ℃, the secondary desiliconization time is 1～2h.
7. method according to claim 1 is characterized in that, the weight of the described non-hydrate sodium metasilicate of step 3) is 5～10% of secondary desiliconization liquid gross weight.
8. method according to claim 1 is characterized in that, cooling step described in the step 3) is: beginning that cooling rate is 3～5 ℃/h in 2 hours, is cooling naturally after 2 hours.
9. method according to claim 1 is characterized in that, the described solid-liquid separation of step 4) adopts spin-on filter device to finish.
10. according to claim 1 or 9 described methods, it is characterized in that the non-hydrate sodium metasilicate that obtains in the step 4) is as crystal seed.
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Cited By (3)
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| CN104973607A (en) * | 2015-07-30 | 2015-10-14 | 江苏南大环保科技有限公司 | Method for continuous extraction production of instant sodium silicate from fly ash |
| CN110627077A (en) * | 2019-11-05 | 2019-12-31 | 中国科学院过程工程研究所 | Method for preparing sodium silicate by using sodium nitrate |
| CN116282053A (en) * | 2022-09-09 | 2023-06-23 | 天津大学 | Method for preparing high-alumina-silica-ratio low-impurity primary crystal mullite by using high-alumina fly ash |
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| US4029736A (en) * | 1973-06-07 | 1977-06-14 | Garegin Sarkisovich Melkonian | Processing pearlite to obtain metal silicates |
| CN101786635A (en) * | 2010-03-17 | 2010-07-28 | 朔州市润泽投资发展有限公司 | Method for preparation of sodium metasilicate pentahydrate by fly ash |
| CN101837985A (en) * | 2010-05-07 | 2010-09-22 | 南昌大学 | Preparation method of sodium metasilicate nonahydrate |
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| US3840348A (en) * | 1971-05-10 | 1974-10-08 | Philadelphia Quartz Co | Crystallizing alkali metal contact with silicate droplets in countercurrent air flow |
| US4029736A (en) * | 1973-06-07 | 1977-06-14 | Garegin Sarkisovich Melkonian | Processing pearlite to obtain metal silicates |
| CN101786635A (en) * | 2010-03-17 | 2010-07-28 | 朔州市润泽投资发展有限公司 | Method for preparation of sodium metasilicate pentahydrate by fly ash |
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Cited By (4)
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| CN104973607A (en) * | 2015-07-30 | 2015-10-14 | 江苏南大环保科技有限公司 | Method for continuous extraction production of instant sodium silicate from fly ash |
| CN104973607B (en) * | 2015-07-30 | 2017-10-20 | 江苏南大环保科技有限公司 | A kind of method that continuous extraction from flyash produces quick dissolved sodium silicate |
| CN110627077A (en) * | 2019-11-05 | 2019-12-31 | 中国科学院过程工程研究所 | Method for preparing sodium silicate by using sodium nitrate |
| CN116282053A (en) * | 2022-09-09 | 2023-06-23 | 天津大学 | Method for preparing high-alumina-silica-ratio low-impurity primary crystal mullite by using high-alumina fly ash |
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