CN101941704A - New method for preparing silicon dioxide by utilizing rice hull ash - Google Patents

New method for preparing silicon dioxide by utilizing rice hull ash Download PDF

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Publication number
CN101941704A
CN101941704A CN 201010271232 CN201010271232A CN101941704A CN 101941704 A CN101941704 A CN 101941704A CN 201010271232 CN201010271232 CN 201010271232 CN 201010271232 A CN201010271232 A CN 201010271232A CN 101941704 A CN101941704 A CN 101941704A
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China
Prior art keywords
rice hull
silicon
hull ash
ammonium fluoride
ammonia
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Pending
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CN 201010271232
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Chinese (zh)
Inventor
王子忱
马晓宇
朱燕超
郭玉鹏
丁雪峰
赵旭
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Jilin University
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Jilin University
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Abstract

The invention discloses a new method for preparing silicon dioxide by utilizing rice hull ash, comprising the following steps: neutralizing and dissolving the soluble impurities in the rice hull ash by utilizing a sulfuric acid solution; adding an ammonium fluoride solution in proportion; heating and dissolving to generate ammonium fluosilicate and discharge ammonia; modulating the concentration of the ammonia water to be 10-30wt% by the ammonia generated in the water recovering reaction; placing into a seal stillpot; regulating the temperature to be 50-90 DEG C; adding the ammonium fluosilicate solution into the ammonia water in proportion; separating out the sedimentation; ageing for 0.5-3h; filtering and performing solid-liquid separation; returning the filter liquor to a silicon dissolving procedure for recycling after the filter liquor concentration is adjusted; and washing and drying the filter cakes to obtain the silicon dioxide. The method of the invention takes the regenerated resource rice hull ash as a silicon source, and adopts constant-voltage low-temperature liquid phase dissolving silicon; and the reactant ammonium fluoride and the by-product ammonia can be recycled, which not only saves the energy consumption and lowers the cost, but also has no other by-product generation and no greenhouse gas emission, thus belonging to a low-carbon green new process.

Description

A kind of rice hull ash prepares the novel method of silicon-dioxide
Technical field
The present invention relates to the novel method that a kind of rice hull ash prepares silicon-dioxide, being specifically related to the rice hull ash is that silicon source, Neutral ammonium fluoride are that solvent prepares the novel method that silicon-dioxide and solvent Neutral ammonium fluoride and by product ammonia recycle utilize.
Background technology
1. utilizing biomass resource to produce silicon-dioxide is the raw material trend that adopts renewable plant resources
At present, world energy sources and crisis of resource make the development and utilization of renewable resources become a focus.Plant/farm crop base renewable resources is particularly developed country's research and the trend utilized both at home and abroad at present, and it will become replenishing and substituent of following nonrenewable resource, changes current to the dependence situation of the nonrenewable resource of minimizing day by day.The incoming stock market of renewable resources has become the important component part of countries in the world resource strategy.
Silicon-dioxide is a kind of application Chemicals very widely, can be used for industries such as rubber, plastics, paint, printing ink, agricultural chemicals, medicine, food, feed, papermaking.Its maximum purposes is that consumption accounts for more than 75% of its ultimate production as reinforced filling.Byproduct after rice husk is processed as paddy, mainly as the primary fuel utilization, the rice hull ash after the burning is little because of its density, volume is big, and environment has been caused pollution, most of at present not processing; Rice husk is after burning, and its ash content is looked the combustion conditions difference and contained 60~95% soft silicas, is the desirable feedstock that is used to produce silicon-dioxide series product, has purity height, renewable, superiority condition that cost is low.Particularly fewer and feweri at high-grade silica sand raw material, high-purity siliceous reinforcing agent lacks under the hard situation of raw material sources, guarantees that the Sustainable development of high-grade white carbon black industry is significant.
2. utilizing explained hereafter silicon-dioxide capable of circulation is to reduce the technology trends that pollutes, protects environment
The traditional method of producing silicon-dioxide is to place reverberatory furnace 1300~1500 ℃ of high-temperature fusion silica sand, soda ash, produces water glass and discharges carbon dioxide; Become rare sodium silicate solution with water-soluble boiling then, use the sulfuric acid neutralization precipitation again, after washing, filter, dry, pulverizing process and silica product.1 ton of silicon-dioxide of the every production of this traditional technology will consume 0.51 ton sulfuric acid and 0.53 ton soda ash, discharges 0.23 ton of carbon dioxide simultaneously and produces 20 tons of waste water (containing 0.74 ton of sodium sulfate).Not only expend a large amount of industrial chemicals, energy consumption is big, the cost height, and produce a large amount of waste water and carbon dioxide, contaminate environment, aggravation Greenhouse effect.
3. domestic and international patent application and authorization conditions
The domestic patent CN1036746A that relevant Neutral ammonium fluoride is produced silicon-dioxide has announced a kind of novel process of producing white carbon black with silica sand, with silica sand and solid NH 4F generates the ammonium silicofluoride solid through pyroreaction, obtains white carbon black again by the ammonium fluoride solution dissolving, and through heavyization of neutralization with ammoniacal liquor, simultaneously ammonium fluoride solution is discharged the reaction system condensing crystal.It is the method for the white carbon black of raw material aminating reaction system with silicofluoric acid and ammoniacal liquor that patent CN101139094A discloses a kind of, and wherein ammoniacal liquor adds step by step, filters proceed step by step, obtains white carbon black through washing drying.It is raw material with silicofluoric acid or ammonium silicofluoride and ammoniacal liquor that patent CN100577567C discloses a kind of, ammoniacal liquor and ammonium silicofluoride or silicofluoric acid rapid reaction are made the white carbon black crystal seed, and based on the white carbon black crystal seed, water, silicofluoric acid or ammonium silicofluoride and ammoniacal liquor are reacted, make white carbon black precipitation and ammonium fluoride solution.
Problems such as it is the molten silicon difficulty of raw material that above method exists respectively with the silica sand, needs pyroreaction, and energy consumption is big, is raw material with silicofluoric acid or ammonium silicofluoride, and raw material sources are limited.The present invention is the silicon source with the biomass rice hull ash, is dissolution with solvents silicon-dioxide with the silicofluoric acid, and the ammonium fluosilicate solution that obtains is added drop-wise to the silica product of preparation good dispersity in the ammonia soln.
Summary of the invention
The present invention be a kind of be the novel method that solvent prepares silicon-dioxide with rice hull ash as silicon source, Neutral ammonium fluoride, the particularly novel method utilized of reactant Neutral ammonium fluoride and by product ammonia recycle.The technical solution used in the present invention is:
A kind of rice hull ash prepares the novel method of silicon-dioxide, and its concrete steps are as follows:
(1) with rice hull ash with water-dispersion after, be neutralized to pH=7 with sulphuric acid soln, dissolve wherein dissolvable oxides and other trace metal impurities, filter, filtrate is as plant ash fertilizer, the filter residue washing is stand-by.
(2) be filter residue in the step (1) and concentration that the ammonium fluoride aqueous solution of 1~5mol/L is by SiO 2With NH 4The mol ratio of F is that 1: 7~15 ratio is put in the reactor, and the heating thermal source transfers to 100~150 ℃, reaction 1~4h, and water reclaims the ammonia that produces in the reaction simultaneously; After reaction finishes, the heat filtering solid-liquid separation, filtrate is as the raw material of preparation silicon-dioxide, and filter residue further carries out activation treatment and prepares top-grade active carbon.
(3) concentration is that the ammoniacal liquor of 10~30wt% places airtight stillpot, and temperature adjustment to 50~90 ℃ join gained filtrate in the step (2) in the ammoniacal liquor in proportion, separate out precipitation, ageing 0.5~3h filters solid-liquid separation, filtrate for later use, filter cake get silica product through washing, drying.
The invention is characterized in that filtrate is mainly contained ammonium fluoride solution in the step (3), come back to participate in the step (2) after the concentrated adjustment of its process concentration and react recycle; The water that produces in the thickener enters receptor and is used to absorb ammonia.
The invention is characterized in that Neutral ammonium fluoride and rice hull ash reaction generate ammonia, return step (3) after the water recovery adjustment concentration and be used for precipitated silica, recycle.
Main chemical reactions principle of the present invention is:
6NH 4F+SiO 2→(NH 4) 2SiF 6+4NH 3+2H 2O
(NH 4) 2SiF 6+4NH 3+(n+2)H 2O→6NH 4F+SiO 2+nH 2O
The traditional technology reaction principle of white carbon black production is:
Na 2O·3.2SiO 2+4H 2SO 4→3.2SiO 2+4Na 2SO 4+H 2O
Compare with traditional technology, advance of the present invention is:
1. change silica sand (SiO 2) high-temperature fusion (1300~1500 ℃) produces the traditional technology of white carbon black (silicon-dioxide), adopts the molten silicon of atmospheric low-temperature liquid phase, saves facility investment 75%, reduces production energy consumption 75%, no carbon dioxide tail gas generation belongs to the energy-saving and emission-reduction novel process;
2. be the silicon source with the renewable resources rice hull ash, it is fewer and feweri to have solved high-grade silica sand raw material, and high-purity siliceous reinforcing agent lacks the difficulty of raw material sources, guarantees the Sustainable development of white carbon black industry;
3. solvent Neutral ammonium fluoride and the equal reusable edible of by product ammonia have not only reduced production cost, and have not used sulfuric acid, do not have other by product and produce discharging, and no greenhouse gas emission belongs to low-carbon (LC) environmental protection novel process.
4. the ammonium fluosilicate solution that obtains is joined in the ammonia soln, silicon-dioxide in alkaline environment nucleation, growing up is particle, has avoided the colloidal particle generation, has guaranteed quality product.
Description of drawings
Figure is a preparation method's of the present invention process flow diagram.
Embodiment
Further set forth the present invention below in conjunction with specific examples.
Embodiment one:
Press SiO 2With NH 4The mol ratio of F is 1: 15 a ratio, take by weighing the rice hull ash of 2kg pickling, the ammonium fluoride solution that concentration is 4mol/L joins in the reactor, thermal source transfers to 140 ℃ of thermostatically heating, backflow stirring reaction 3 hours, filtered while hot, filtrate joins in the ammoniacal liquor that concentration is 30wt%, separate out precipitation, 60 ℃ of constant temperature ageing 1h filter, washing, 120 ℃ of dryings 12 hours, make the preparing spherical SiO 2 that median size is 60nm, productive rate is 96.9%.
Embodiment two:
The concentration that changes Neutral ammonium fluoride is 3mol/L, and other condition such as embodiment one make the preparing spherical SiO 2 that median size is 65nm, and productive rate is 93.8%.
Embodiment three:
Change SiO 2With NH 4The mol ratio of F is 1: 8, and other condition such as embodiment one make the preparing spherical SiO 2 that median size is 65nm, and productive rate is 84.6%.
Embodiment four:
Change thermal source Heating temperature to 120 ℃, other condition such as embodiment one make the preparing spherical SiO 2 that median size is 60nm, and productive rate is 94.6%.
Embodiment five:
The change reaction times is 2h, and other condition such as embodiment one make the preparing spherical SiO 2 that median size is 60nm, and productive rate is 96.2%.
Embodiment six:
The change ammonia concn is 15wt%, and other condition such as embodiment one make the preparing spherical SiO 2 that median size is 100nm, and productive rate is 96.8%
Embodiment seven:
Changing heavyization temperature is 90 ℃, and other condition such as embodiment one make the preparing spherical SiO 2 that median size is 70nm, and productive rate is 96.5%
Embodiment eight:
Changing the heavyization time is 2h, and other condition such as embodiment one make the preparing spherical SiO 2 that median size is 85nm, and productive rate is 96.6%.

Claims (3)

1. one kind is the green circulation technology of feedstock production silicon-dioxide with rice hull ash as silicon source, Neutral ammonium fluoride, and its concrete steps are as follows:
(1) with rice hull ash with water-dispersion after, be neutralized to pH=7 with sulphuric acid soln, dissolve wherein dissolvable oxides and other trace metal impurities, filter, filtrate is as plant ash fertilizer, the filter residue washing is stand-by.
(2) be filter residue in the step (1) and concentration that the ammonium fluoride aqueous solution of 1~5mol/L is by SiO 2With NH 4The mol ratio of F is that 1: 7~15 ratio is put in the reactor, is heated to 100~150 ℃, reaction 1~4h, and water reclaims the ammonia that produces in the reaction simultaneously; After reaction finishes, the heat filtering solid-liquid separation, filtrate is as the raw material of preparation silicon-dioxide, and filter residue further carries out activation treatment and prepares top-grade active carbon.
(3) be that the ammoniacal liquor of 10~30wt% places airtight stillpot with concentration, temperature adjustment to 50~90 ℃ add gained filtrate in the step (2) in proportion, separate out precipitation, ageing 0.5~3h filters solid-liquid separation, filtrate for later use, filter cake get nano silicon through washing, drying.
2. a kind of rice hull ash as claimed in claim 1 prepare silicon-dioxide novel method, it is characterized in that: Neutral ammonium fluoride and rice hull ash reaction generate ammonium silicofluoride and ammonia, behind the filtering separation breeze, ammonium fluosilicate solution joins in the ammoniacal liquor, generate precipitation of silica and ammonium fluoride solution, filtration obtains silica filter cake and ammonium fluoride solution, and ammonium fluoride solution returns step (2) recycle after concentrating, and the water that concentrates generation returns step (2) and is used to absorb ammonia.
3. a kind of rice hull ash as claimed in claim 1 prepare silicon-dioxide novel method, it is characterized in that: the reaction of Neutral ammonium fluoride and rice hull ash generates ammonia, water reclaims to adjust and returns step (3) after the concentration and be used for precipitated silica, recycle.
CN 201010271232 2010-09-03 2010-09-03 New method for preparing silicon dioxide by utilizing rice hull ash Pending CN101941704A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502637A (en) * 2011-10-08 2012-06-20 江苏佳宇资源利用股份有限公司 Method for removing silicon dioxide (SiO2) component in silicon carbide micropowder
CN102602941A (en) * 2012-03-22 2012-07-25 武汉科技大学 Method for protecting original porous texture of rice hulls at high temperature
CN102616793A (en) * 2012-03-26 2012-08-01 阳光凯迪新能源集团有限公司 Method for eliminating metal ions in rice hulls by utilizing industrial flue gas
CN102730703A (en) * 2012-06-15 2012-10-17 武汉凯迪工程技术研究总院有限公司 Method for inexpensive preparation of surface modified nano-silicon dioxide with rice husks
CN103663476A (en) * 2013-12-21 2014-03-26 瓮福(集团)有限责任公司 Precipitation method for white carbon black production
RU2567954C1 (en) * 2014-08-01 2015-11-10 Общество с ограниченной ответственностью "Экологические Системы" METHOD OF OBTAINING SYNTHETIC SiO2 (SILICON DIOXIDE)
CN106267911A (en) * 2016-08-25 2017-01-04 周荣 A kind of preparation method of plant base organic silicon defoamer
CN106495166A (en) * 2016-10-09 2017-03-15 常州亚环环保科技有限公司 A kind of preparation method of rice husk base micro-nano structure porous silica
CN106976876A (en) * 2017-06-01 2017-07-25 江汉大学 A kind of method that desiliconization technology in situ prepares rice husk matrix activated carbon
CN107459037A (en) * 2017-08-02 2017-12-12 四川大学 A kind of method of low temperature preparation carbon material coproduction fertilizer
CN108502891A (en) * 2018-04-26 2018-09-07 上海理工大学 The method for preparing silica using the waste bottom ash of sugar industry

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1319561A (en) * 2001-04-10 2001-10-31 夏克立 Method for producing fluoride and silicon dioxide
CN101417798A (en) * 2008-11-26 2009-04-29 吉林大学 Paddy hull burned gas and waste residue comprehensive utilization method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1319561A (en) * 2001-04-10 2001-10-31 夏克立 Method for producing fluoride and silicon dioxide
CN101417798A (en) * 2008-11-26 2009-04-29 吉林大学 Paddy hull burned gas and waste residue comprehensive utilization method

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102502637A (en) * 2011-10-08 2012-06-20 江苏佳宇资源利用股份有限公司 Method for removing silicon dioxide (SiO2) component in silicon carbide micropowder
CN102602941A (en) * 2012-03-22 2012-07-25 武汉科技大学 Method for protecting original porous texture of rice hulls at high temperature
CN102616793A (en) * 2012-03-26 2012-08-01 阳光凯迪新能源集团有限公司 Method for eliminating metal ions in rice hulls by utilizing industrial flue gas
WO2013143377A1 (en) * 2012-03-26 2013-10-03 阳光凯迪新能源集团有限公司 Method utilizing industrial flue gas for removing metal ions from rice hulls
CN102616793B (en) * 2012-03-26 2014-02-26 阳光凯迪新能源集团有限公司 Method for eliminating metal ions in rice hulls by utilizing industrial flue gas
RU2567629C1 (en) * 2012-03-26 2015-11-10 Саншайн Кайди Нью Энерджи Груп Ко., Лтд. Method of applying industrial furnace gas for removal of metal ions from husk of rice grains
CN102730703B (en) * 2012-06-15 2014-05-28 武汉凯迪工程技术研究总院有限公司 Method for inexpensive preparation of surface modified nano-silicon dioxide with rice husks
CN102730703A (en) * 2012-06-15 2012-10-17 武汉凯迪工程技术研究总院有限公司 Method for inexpensive preparation of surface modified nano-silicon dioxide with rice husks
CN103663476B (en) * 2013-12-21 2016-03-23 瓮福(集团)有限责任公司 Intermediate processing in a kind of white carbon black production
CN103663476A (en) * 2013-12-21 2014-03-26 瓮福(集团)有限责任公司 Precipitation method for white carbon black production
RU2567954C1 (en) * 2014-08-01 2015-11-10 Общество с ограниченной ответственностью "Экологические Системы" METHOD OF OBTAINING SYNTHETIC SiO2 (SILICON DIOXIDE)
CN106267911A (en) * 2016-08-25 2017-01-04 周荣 A kind of preparation method of plant base organic silicon defoamer
CN106267911B (en) * 2016-08-25 2018-07-24 济南实成有机硅科技有限公司 A kind of preparation method of plant base organic silicon defoamer
CN106495166A (en) * 2016-10-09 2017-03-15 常州亚环环保科技有限公司 A kind of preparation method of rice husk base micro-nano structure porous silica
CN106976876A (en) * 2017-06-01 2017-07-25 江汉大学 A kind of method that desiliconization technology in situ prepares rice husk matrix activated carbon
CN106976876B (en) * 2017-06-01 2018-11-02 江汉大学 A kind of method that original position desiliconization technology prepares rice husk matrix activated carbon
CN107459037A (en) * 2017-08-02 2017-12-12 四川大学 A kind of method of low temperature preparation carbon material coproduction fertilizer
CN108502891A (en) * 2018-04-26 2018-09-07 上海理工大学 The method for preparing silica using the waste bottom ash of sugar industry

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Application publication date: 20110112