CN1736863A - Wet method for producing polymerized alumnium choride and high module liquid sodium silicate from coal serial kaolin - Google Patents
Wet method for producing polymerized alumnium choride and high module liquid sodium silicate from coal serial kaolin Download PDFInfo
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- CN1736863A CN1736863A CN 200410058137 CN200410058137A CN1736863A CN 1736863 A CN1736863 A CN 1736863A CN 200410058137 CN200410058137 CN 200410058137 CN 200410058137 A CN200410058137 A CN 200410058137A CN 1736863 A CN1736863 A CN 1736863A
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Abstract
The invention provides a process for producing polymerized aluminum chloride as water purification agent and liquid sodium silicate simultaneously, wherein coal series kaolinite rocks are used as the main raw material for acid pickling, dissolving with acid and alkali.
Description
The invention belongs to water purification agent polymerize aluminum chloride and broad-spectrum liquid sodium silicate combine production method.Particularly be main raw material, by the method for acidleach and sour molten slag difference thickness and molten production polymerize aluminum chloride of alkali and high-module liquid sodium silicate with the coal series kaolin rock.
Coal series kaolin rock is a kind of of coal gangue, is present in roof, base plate or the interlayer.Except that combustible volatile matter and fixed carbon, its component is near Al
2O
32SiO
22H
2The desirable component of the kaolinite of O.For utilizing aluminium and Si oxide wherein, people have carried out big quantity research.A kind of approach is molten by acid, makes Al
2O
3Become polymerize aluminum chloride or Tai-Ace S 150.And be to produce the polymerize aluminum chloride person often to take to use merely hydrochloric acid.Many investigators think that the residue of acid after molten just can become the high reinforcement precipitated silica of tool (white carbon black), though in fact at SiO
2Content, index aspects such as specific surface area have all reached the national standard of precipitated silica, but find that its reinforcing effect is very poor in the rubber experiment.This is because these investigators have ignored high reinforcement white carbon black and must have good dispersibility, and is hanged down under the pH value condition owing to being in all the time by the molten silicon-dioxide that obtains of simple acid, and its agglomeration process makes cluster of grains quite fine and close, and has destroyed dispersibility.First acid just to have occurred molten thereupon, and alkali is molten again, with the method for the molten production liquid sodium silicate of simple alkali.This method is to adopt the method for typical wet method system liquid sodium silicate, promptly uses NaOH solution dissolving acid molten slag.Owing to still have Al in many sour molten slages
2O
3, Fe
2O
3Deng composition, they tend to by the alkali lye stripping under the temperature condition about 90 ℃, and form red mud when pH value is low slightly, thereby this method is difficult to produce the high-module liquid sodium silicate.This situation that can not make high-modulus sodium silicate with wet method system water glass method is consistent in fact.For addressing this problem, the research worker who has adopts the twice molten technology of adverse current acid to improve the solubility rate of aluminium, iron in the molten stage of acid, the interference that minimizing is molten to alkali, doing has like this increased sour molten equipment and operation, and for coal series kaolin rock, can not all remove volatile matter and fixed carbon through low temperature calcination, their existence makes aluminium, silicon leaching yield all be difficult to the degree that reaches very high, and nature can not be at the industrial-scale production high-modulus sodium silicate.
The present invention be with coal series kaolin rock through fluidized bed calcination stove calcining, levigate, in hydrochloric acid and sulfuric acid mixed solution and the immersion liquid of part recycle acid, react, isolating product liquid except that part circulates through adding Wingdale or calcium aluminate is polymerized to polymerize aluminum chloride; Isolating slag separates by thickness, and its coarse fodder reacts the low modulus liquid sodium silicate of generation with alkali lye in advance under 75 ℃～80 ℃ conditions, and the silicon gel of this liquid and thin slag and adjustment process generation reacts under 90 ℃ again and generates the high-module liquid sodium silicate.The saturated lime clear liquid of desirable its part adding carried out causticization when low modulus water glass was on the high side, reclaim alkali lye, its sedimentary Calucium Silicate powder and dilute sulphuric acid reaction, elimination calcium sulfate and ferric sulfate get the acid-sol of silicon, and low modulus liquid sodium silicate is heightened its pH value and the silicon gel occurred.This silicon gel can be mended height and touch in several liquid sodium silicate production processes, guarantees the accuracy of product modulus.
Advantage of the present invention is:
1) calcine with the fluidized bed calcination kiln: the investigator generally recognizes the importance of calcining temperature, and assert that 650 ℃～750 ℃ is the molten optimum calcinating temperature of acid.In the existing calciner, the fluidized bed calcination kiln be unique can be at the equipment of 650 ℃～750 ℃ of accurate temperature controls.
2) with hydrochloric acid and sulfuric acid mixed solution and part recycle acid solution reaction: at first be cheap than hydrochloric acid at many regional sulfuric acid, vitriolic corrodibility also is lower than hydrochloric acid.The more important thing is when adjusting basicity and calcium sulfate precipitation can occur with Wingdale or calcium aluminate.So both improve basicity and also improved Al simultaneously
2O
3Content guarantees that these two important indicators reach the premium grads standard simultaneously.As leaching with hydrochloric acid merely, polymerization process will produce CaCl
2Though, improved basicity, reduced Al
2O
3, and make solid phase prod be easy to deliquescence.Part pickling liquor cyclically utilizing is intended to increase solid-to-liquid ratio, is convenient to stir and separate; Also can improve the initial basicity of sour molten product, reduce sour consumption.
3) thickness grading of sour molten slag: thickness particle component difference, fine particle SiO
2The purity height can directly enter the high-modulus sodium silicate production process.
4) the low modulus alkali of coarse particles low temperature is molten: with 90 ℃～95 ℃ comparisons commonly used, though the silicon solubility rate descends to some extent during low temperature, the solubility rate of aluminium reduces more obvious, and the water glass that can quicken stripping about 90 ℃ wraparound generation Na again
2OAl
2O
3NSiO
2Side reaction, influence silicon yield and quality product.
5) secondary reaction of high-module: the modulus parameter is hanged down in a molten use of alkali, at first is to have improved total alkali content and liquid-solid ratio, and all useful in stirring, separation, solubility rate is also high.Too much alkali number can be adjusted by causticization with from acid-sol system silicon gel.And add fine particle in the secondary reaction and the silicon gel can generate the high-module product smoothly.Therefore this technology has been taken into account the advantage of height modulus reaction.Raw material is also saved.
The high-module liquid sodium silicate can be again the basic material of silicon series product etc. directly as commodity selling both.
The present invention is achieved in that
1) calcining: coal series kaolin rock is broken in advance to-5 orders.Send into circulating fluidized bed calcinator, the average stop 2 hours in 650 ℃～750 ℃ stove.Refrigerative calcining material is by levigate extremely-200 orders.
2) acid is molten: levigated calcining material is made mud with sour molten slag wash water metering send into reactor.Liquid-solid ratio is 2.5～3,30% hydrochloric acid in the acid solution of adding: 93% sulfuric acid: recycle acid immersion liquid: the volume ratio of water (containing the slurrying water) is 1: (0.1～0.3): (1.5～2): (1～1.2).1.5～3 hours reaction times, 130 ℃ of temperature of reaction (compressive reaction).Reactant is discharged into settling tank, gets the suspension press filtration after 0.5～2 hour, and filtrate is partly circulated, part is gone to polymerize aluminum chloride workshop section, filtrate is reacted with Wingdale that is metered into or calcium aluminate in polymerization reaction kettle, and polymeric reaction temperature is 100 ℃～150 ℃, 1～2 hour reaction times.Al in the dry polymer
2O
3Content surpasses 32%, and basicity surpasses 60%.After cleaning, filter cake send high-modulus sodium silicate reaction workshop section.Sediment is cleaned and is sent alkali molten workshop section.
3) alkali is molten: the molten reactor of alkali is sent in sour molten sediment metering, and concentration of lye is 8～13%, and liquid-solid ratio is 3～5, and temperature of reaction is 75 ℃～80 ℃, 60～90 minutes reaction times.Get filtrate through leaf filter and send low modulus water glass storage tank.
4) causticization and system silica gel: get the molten low modulus liquid sodium silicate of 0～75% alkali with CaO and SiO
2Equivalence ratio be 0.8～0.95 to add saturated lime clear liquid, boiled 1～2 hour, filtrate uses alkali lye, Calucium Silicate powder filter cake to send silicon gel workshop section for circulation.Calucium Silicate powder adds in the dilute sulphuric acid gradually, keeps PH≤2,50 ℃ of temperature of reaction.Filter Calucium Silicate powder, in filtrate, add low modulus liquid sodium silicate, adjust PH=3～5.40 ℃～50 ℃ of temperature of reaction, ageing 2 hours, the elimination clear liquid gets the silicon gel.
5) the high-module liquid sodium silicate is produced: siliceous alkali lye is heated to 90 ℃, is metered into molten thin slag of acid and silicon gel, 30 minutes reaction times.
Claims (5)
1. with coal series kaolin rock wet production polymerize aluminum chloride and high-module liquid sodium silicate technology, it is characterized in that following steps:
1) coal series kaolin rock through fluidized bed calcination stove calcining, levigate, with hydrochloric acid and sulfuric acid mixture liquid reaction, its pickling liquor is polymerized to polymerize aluminum chloride through adding Wingdale or Calucium Silicate powder;
2) acid leaching residue divides thickness two portions, and the reaction of its coarse fodder and alkali (NaOH) liquid generates low modulus liquid sodium silicate, and this low modulus liquid sodium silicate reacts with thin acid leaching residue and silicon gel again and generates the high-module liquid sodium silicate.When low modulus liquid silicic acid sodium amount is on the high side, get the low modulus liquid sodium silicate of its 0～75% alkali lye through adding saturated lime clear liquid causticization, reclaim alkali lye; Sedimentary Calucium Silicate powder and dilute sulphuric acid react the acid-sol of silicon, heighten pH value with low modulus liquid sodium silicate again and produce the silicon gel, this silicon gel can be mended in the high-module liquid sodium silicate production process, guarantees the modulus value of liquid sodium silicate.
2. according to claim 1, it is characterized in that coal series kaolin rock is crushed to 5 orders, mean residence time is 2 hours in circulating fluidized bed calcinator, 650 ℃～750 ℃ of furnace temperature.The refrigerative calcining is expected by levigate to 200 orders.
3. according to claim 1, the liquid-solid ratio that it is characterized in that acidleach is 2.5～3,30% hydrochloric acid in the used acid solution: 93% sulfuric acid: recycle acid immersion liquid: the volume ratio of water (containing the slurrying water) is 1: (0.1～0.3) (1.5～2): (1～1.2).1.5～3 hours reaction times, 130 ℃ of temperature of reaction (compressive reaction).
4. according to claim 1, it is characterized in that pickling liquor and slag precipitate 0.5～2 hour in settling tank, its suspension is through press filtration, filtrate is reacted with the Wingdale that is metered in polymerization reaction kettle, polymeric reaction temperature is 100 ℃～150 ℃, 1～2 hour reaction times, drying.Al in the polymkeric substance
2O
3Content surpasses 32%, and basicity surpasses 60%.
5. according to claim 1, it is characterized in that alkali molten be 8～13% with NaOH content with alkali lye, solid-to-liquid ratio is 3～5, temperature of reaction is 75 ℃～80 ℃, the reaction times is 60～90 minutes.
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|---|---|---|---|
| CN 200410058137 CN1736863A (en) | 2004-08-16 | 2004-08-16 | Wet method for producing polymerized alumnium choride and high module liquid sodium silicate from coal serial kaolin |
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| CN 200410058137 CN1736863A (en) | 2004-08-16 | 2004-08-16 | Wet method for producing polymerized alumnium choride and high module liquid sodium silicate from coal serial kaolin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905898A (en) * | 2010-08-03 | 2010-12-08 | 常州友邦净水材料有限公司 | Utilization method for polymeric aluminium reaction residues |
| CN102225770A (en) * | 2011-03-23 | 2011-10-26 | 张振慧 | Wet preparation method of special water glass for petrochemical catalyst |
| CN108585779A (en) * | 2018-05-04 | 2018-09-28 | 中国科学院过程工程研究所 | A method of preparing Al-Si composites using gasification slag |
| CN114314778A (en) * | 2020-09-30 | 2022-04-12 | 中国科学院过程工程研究所 | Method for producing water purifying agent and white carbon black by roasting-free and reinforced acid leaching coal gangue |
-
2004
- 2004-08-16 CN CN 200410058137 patent/CN1736863A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101905898A (en) * | 2010-08-03 | 2010-12-08 | 常州友邦净水材料有限公司 | Utilization method for polymeric aluminium reaction residues |
| CN101905898B (en) * | 2010-08-03 | 2012-06-27 | 常州友邦净水材料有限公司 | Utilization method for polymeric aluminium reaction residues |
| CN102225770A (en) * | 2011-03-23 | 2011-10-26 | 张振慧 | Wet preparation method of special water glass for petrochemical catalyst |
| CN102225770B (en) * | 2011-03-23 | 2015-08-19 | 张振慧 | The method of wet method Effect of Catalysis In Petrochemistry agent dedicated water glass |
| CN108585779A (en) * | 2018-05-04 | 2018-09-28 | 中国科学院过程工程研究所 | A method of preparing Al-Si composites using gasification slag |
| CN108585779B (en) * | 2018-05-04 | 2021-10-15 | 中国科学院过程工程研究所 | Method for preparing aluminum-silicon composite material by using gasified slag |
| CN114314778A (en) * | 2020-09-30 | 2022-04-12 | 中国科学院过程工程研究所 | Method for producing water purifying agent and white carbon black by roasting-free and reinforced acid leaching coal gangue |
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