CN102815728A - Method for preparing nano-sized magnesium hydroxide and nano-silica by utilization of boron mud - Google Patents

Method for preparing nano-sized magnesium hydroxide and nano-silica by utilization of boron mud Download PDF

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Publication number
CN102815728A
CN102815728A CN2012101975103A CN201210197510A CN102815728A CN 102815728 A CN102815728 A CN 102815728A CN 2012101975103 A CN2012101975103 A CN 2012101975103A CN 201210197510 A CN201210197510 A CN 201210197510A CN 102815728 A CN102815728 A CN 102815728A
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nano
magnesium hydroxide
reaction
boron mud
sized magnesium
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CN2012101975103A
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郑水林
宋贝
狄永浩
侯会丽
刘超
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China University of Mining and Technology Beijing CUMTB
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China University of Mining and Technology Beijing CUMTB
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Abstract

The invention relates to a method for preparing nano-sized magnesium hydroxide and nano-silica by the utilization of boron mud, comprising the following steps of: adding calcined boron mud into concentrated sulfuric acid for acid leaching and dissociation; carrying out solid-liquid separation on a pickle liquor which has undergone acid leaching and dissociation; oxidizing a filtrate which has undergone solid-liquid separation and using alkali lye for precipitation separation of iron hydroxide; adding the iron-removed filtrate into a particle surface modifier and alkali lye to prepare nano-sized magnesium hydroxide; carrying out alkali dissolution by the use of acid slag obtained after solid-liquid separation, filtering, and adding a particle blocker and an acid solution into a filtrate to prepare nano-silica. According to the technology, main ingredients of magnesium oxide and silica in boron mud can be highly efficiently and comprehensively utilized to prepare the product with high added value, and the environmental pollution problem of boron mud can be solved. The magnesium hydroxide prepared in the invention is sheet-shaped nanometer magnesium hydroxide. White carbon black is spherical nanometer white carbon black.

Description

A kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white
Technical field
The present invention relates to a kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white, belong to mineral processing and utilize technical field with solid waste.
Background technology
Boron mud is the waste residue that produces when producing product such as boric acid, borax.Boron mud is light red, and particle is thin, becomes loose shape, and its major ingredient is MgO and SiO 2, and contain a spot of Fe 2O 3, Al 2O 3, CaO, B 2O 3Deng.Because the apparent alkalescence of boron mud, its alkali lye can be added in the underground water, makes the farmland underproduction on every side, can cause the farm crop total crop failure when serious, and tap water is on every side produced pollution.Therefore, it is land occupation not only, and to around the arable land cause severe contamination, the institute's part soil that discharges exhaustion, not even a blade of grass grows.Along with socioeconomic continuous development, the demand of borax, boric acid is increased year by year, the output of boron mud also will increase year by year.The processing of a large amount of boron mud has become one of difficult problem that boron development of resources and boron rock processing industry need to be resolved hurrily at present.
Contain valuable elements such as magnesium, silicon in the boron mud, have higher utility value.Therefore, develop this secondary resource, produce high-quality Marinco H and WHITE CARBON BLACK, all significant to reducing environmental pollution, promote resource recovery and improving the business economic benefit.
The present invention is directed to the present situation of present boron mud pollution on the environment and comprehensive utilization, propose a kind of method of efficiently utilizing Natural manganese dioxide and silica component in the boron mud to prepare nano-sized magnesium hydroxide and Nano carbon white.
Summary of the invention
Boron mud and sulphuric acid soln are leached reaction; With reacted dope filtration, washing to separate the solid-liquid component; In gained filtrating, add suitable oxygenant oxidation Fe wherein 2+After add the iron component in the alkali solution precipitate filtrating; After removing by filter throw outs such as ironic hydroxide, add alkali reaction, add an amount of particle surface modifier simultaneously; Carry out ageing, filtration, washing, drying and the depolymerization of reaction system after the reaction, obtaining simple granularity is that nano level, particle shape are flaky Marinco H powder; Residue behind boron mud and the sulfuric acid reaction and sodium hydroxide are carried out hydro-thermal reaction under the situation of heating, after the reaction product is filtered, filtrating is added add a certain amount of particle barrier agent after water is adjusted to certain concentration, carry out precipitating with acid; With obtaining ball shaped nano level WHITE CARBON BLACK after the ageing of precipitating product, filtration, washing, the drying.
Its process step and principle are following:
(1) boron mud is calcined 0.5~1.5h down for 300~700 ℃ in calcining temperature;
(2) will calcine that back boron mud adds water and sulfuric acid reacts, and obtain the mixed slurry of compositions such as sulfur acid magnesium, Tai-Ace S 150, ferrous sulfate and ferric sulfate, its reaction formula is:
MgO+H 2SO 4→MgSO 4+H 2O
Al 2O 3+3H 2SO 4→Al 2(SO 4) 3+3H 2O
Fe 2O 3+3H 2SO 4→2Fe 2(SO 4) 3+3H 2O
FeO+H 2SO 4→FeSO 4+H 2O
(3) above-mentioned mixed slurry is filtered, transfers to suitable concentration after removing solid residue, add ydrogen peroxide 50 and add alkali reaction to slurry pH value 4~7 after to oxidation of divalent iron ion 15~45min, its reaction formula is following:
H 2O 2+2FeSO 4+H 2SO 4=Fe 2(SO 4) 3+2H 2O
Fe 2(SO 4) 3+6NaOH=2Fe(OH) 3↓+3Na 2SO 4
(4) with after above-mentioned oxidation reaction product filtration, removing ferric hydroxide precipitate, add the particle surface modifier, add alkali reaction to slurry pH value 10~13, get magnesium hydrate precipitate.Its reaction formula is following:
MgSO 4+2NaOH=Mg(OH) 2↓+Na 2SO 4
(5) will contain slurries ageing, filtration, washing, the drying of magnesium hydrate precipitate thing, depolymerization promptly obtains flake nano level magnesium hydroxide products.
(6) solid residue that leaches in the step (2) and caustic soda are reacted under heating condition, generate the slurries that contain water glass, its reaction formula is:
SiO 2·nH 2O+2NaOH=Na 2O·mSiO 2+(n+1)H 2O
(7) with the above-mentioned dope filtration that contains water glass, remove solid residue and add water move to 10~30 ° of solution degree Beaume; Descend and flow to add sour precipitating to slurry pH value 3~7 at 30~90 ℃; Simultaneously under agitation add the particle barrier agent, obtain the hydrated SiO 2 deposition, its reaction formula is following:
Na 2O·mSiO 2+H 2SO 4+nH 2O→mSiO 2·nH 2O +Na 2SO 4
This reaction product ageing, filtration, washing, drying, depolymerization are promptly got ball shaped nano level WHITE CARBON BLACK product.
Boron mud described in the step (1), its granularity are 50~500 orders.
Particle surface modifier described in the step (4) is one of titanic acid ester, silane, aluminate coupling agent, organosilicon or the combination between them.
Particle barrier agent described in the step (7) is one of polyoxyethylene glycol, aluminate coupling agent, titanate coupling agent, silane coupling agent, organosilicon, OP-10 or the combination between them.
Below be prescription of the present invention and processing condition:
(1) acid is dissolved: calcining boron mud: 96% sulfuric acid: water (mass ratio)=100: 80~160: 120~240,90~120 ℃ of temperature of reaction, reaction times 0.5~3h;
(2) iron removal by oxidation: 30%H 2O 2Consumption be 1%~10% of calcining boron shale amount, 30~80 ℃ of temperature of reaction, ageing 30~60min;
(3) deposition Mg (OH) 2: 30~90 ℃ of temperature of reaction, digestion time 15~60min; The coating materials consumption is 0.3%~5% of a Marinco H quality;
(4) sour molten slag alkali dissolves: sour molten slag: NaOH: water=100: 20~80: 200~400,90~120 ℃ of temperature of reaction, reaction times 1~4h;
(5) hydrated SiO 2 deposition: particle barrier agent consumption is 0.5%~6% of a Nano carbon white quality.
Use the Marinco H of the present invention's preparation to be flake nano level Marinco H, and (the BET specific surface area is less than 70m to have less specific surface area 2/ g), higher degree (Mg (OH) 2Content>98%), dispersiveness and good surface activity; The WHITE CARBON BLACK product is a ball shaped nano level WHITE CARBON BLACK product, and (the BET specific surface area is greater than 200m greatly to have specific surface area and pore volume 2/ g and pore volume are greater than 1.0cm 3/ g), the high (SiO of purity 2Content>98%), the light (bulk density≤0.15g/cm of unit weight 3), characteristic such as dispersiveness and good surface activity.
The accompanying drawing content
Accompanying drawing 1 is technical process of the present invention, and accompanying drawing 2 is the flake nano level Marinco H of embodiment of the invention preparation and the scanning electron microscope analysis result of ball shaped nano level WHITE CARBON BLACK.
Embodiment
Embodiment one:
200g boron mud is calcined 1h down at 600 ℃; Get calcining boron mud 100g, add water 180g, concentration is 96% sulfuric acid 120g, reacts 1.5h down at 95 ℃; Filter the back and separate the solid-liquid component; Adding 5.0g mass concentration is 30% ydrogen peroxide 50 in leach liquor, reacts 15min down at 60 ℃; The pH value of hydro-oxidation sodium solution regulation system is 6.5, ageing 30min; Behind the filtering separation throw out, the degree Beaume of regulator solution is 20 °, adds polyoxyethylene glycol 0.12g, is 13 in the pH value of 80 ℃ of following dropping sodium solution to systems, can obtain flake nano level magnesium hydroxide products after ageing 50min after-filtration, washing, the drying.
Get dry sour lixiviation slag 40g; Add water 120g, solid sodium hydroxide 13g,, remove by filter residue at 95 ℃ of following stirring reaction 1h; Add water the degree Beaume of filtrating is adjusted to 20 °; Add 1.2g silane, 70 ℃ down and drips to add degree Beaume be that 20 ° water glass solution and mass concentration is that 20% sulphuric acid soln reacts, reaction system final pH value is 3.5; Ageing 50min in reaction back filters then, washs, drying and depolymerization promptly get ball shaped nano level WHITE CARBON BLACK product.
Embodiment two:
500kg boron mud is calcined 1h down at 600 ℃; Get calcining boron mud 200kg, add water 360kg, concentration is 96% sulfuric acid 240kg, reacts 1.5h down at 100 ± 5 ℃; Filter the back and separate the solid-liquid component; Adding 10kg mass concentration is 30% ydrogen peroxide 50 in leach liquor, reacts 15min down at 60 ℃; The pH value of hydro-oxidation sodium solution regulation system is 6.5, ageing 30min; Behind the filtering separation throw out, the degree Beaume of regulator solution is 20 °, adds polyoxyethylene glycol 0.24kg, is 13 in the pH value of 80 ℃ of following dropping sodium solution to systems, can obtain flake nano level magnesium hydroxide products after ageing 50min after-filtration, washing, the drying.
Get dry sour lixiviation slag 80kg; Add water 220kg, solid sodium hydroxide 26kg,, remove by filter residue at 100 ± 5 ℃ of following stirring reaction 1h; Add water the degree Beaume of filtrating is adjusted to 20 °; Add 2.4kg silane, 70 ℃ down and drips to add degree Beaume be that 20 ° sodium silicate solution and mass concentration is that 20% sulfuric acid reacts, the last pH value of reaction system is 3.5; Ageing 50min in reaction back filters then, washs, drying and depolymerization promptly get ball shaped nano level WHITE CARBON BLACK product.
Table 1 is embodiment products obtained therefrom physicochemical property detected results.
The check and analysis result of table 1 embodiment sample

Claims (6)

1. method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white is characterized in that its process step is:
(1) boron mud is calcined 1h down at 600 ℃;
(2) will calcine that back boron mud adds water and sulphuric acid soln reacts;
(3) reaction product is filtered separating solid residue;
(4) will filtrate and under 30~80 ℃, add hydrogen peroxide oxidation and alkaline chemical precipitation ironic hydroxide to slurries pH=4~7, and the filtering separation ironic hydroxide;
(5) filtrating after the deironing is added the particle surface modifier, and under 30~90 ℃ of temperature of reaction, add alkali reaction to slurries pH=10~13, after-filtration, washing, drying, depolymerization are accomplished in reaction, nano-sized magnesium hydroxide;
(6) step (3) filter residue hydro-oxidation sodium and water are reacted 1~4h down at 90~120 ℃, and to dope filtration;
(7) will filtrate with sulfuric acid 30~90 ℃ down and stream react to slurries pH=3~7, add the particle barrier agent simultaneously, after-filtration, washing, drying, depolymerization are accomplished in reaction, obtain nano silicon.
2. a kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white according to claim 1; The batching mass ratio that it is characterized in that step (2) is calcining boron mud: 96% sulfuric acid: water (mass ratio)=100: 80~160: 120~240; 90~120 ℃ of temperature of reaction, reaction times 0.5~3h.
3. a kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white according to claim 1 is characterized in that the consumption of ydrogen peroxide 50 is 1%~10% of calcining boron shale amount.
4. a kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white according to claim 1; The particle surface modifier that it is characterized in that step (5) is one of titanic acid ester, silane, aluminate coupling agent, organosilicon or the combination between them, and consumption is 0.3%~5% of a Marinco H quality.
5. a kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white according to claim 1, the batching mass ratio that it is characterized in that step (6) is sour molten slag: NaOH: water=100: 20~80: 200~400.
6. a kind of method of utilizing boric sludge to be equipped with nano-sized magnesium hydroxide and Nano carbon white according to claim 1; The particle barrier agent that it is characterized in that step (7) is one of polyoxyethylene glycol, aluminate coupling agent, titanate coupling agent, silane coupling agent, organosilicon, OP-10 or the combination between them, and consumption is 0.5%~6% of a Nano carbon white quality.
CN2012101975103A 2012-08-31 2012-08-31 Method for preparing nano-sized magnesium hydroxide and nano-silica by utilization of boron mud Pending CN102815728A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103923379A (en) * 2013-01-14 2014-07-16 中国地质大学(北京) Method for preparing fire retardation polymer composite material by using boron mud
CN104446598A (en) * 2014-06-30 2015-03-25 中国地质大学(北京) Flame-retarding heat-insulating material based on boric sludgeand preparation method of flame-retarding heat-insulating material
CN104671262A (en) * 2015-01-30 2015-06-03 李广凡 Light magnesium carbonate prepared by boric sludge acidification method as well as production method and application thereof
CN112316910A (en) * 2020-10-28 2021-02-05 东北大学 Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group
CN112574504A (en) * 2020-11-20 2021-03-30 应急管理部沈阳消防研究所 Aerogel prepared by boron mud waste, flame retardant and modification application of aerogel
CN116282096A (en) * 2023-05-12 2023-06-23 中科镁基(北京)科技有限公司 Comprehensive utilization method of boric sludge

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CN101161591A (en) * 2006-10-09 2008-04-16 中国矿业大学(北京) A method for preparing schistose nanometer magnesium hydroxide and sphericity nanometer white carbon black using zillerite gangue
CN101323452A (en) * 2007-06-11 2008-12-17 肖莹 Method for preparing precipitated silica with boron sludge
CN102030349A (en) * 2010-11-29 2011-04-27 沈阳工业大学 Method for extracting magnesium hydroxide by using boric sludge and treating dye wastewater

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CN101161591A (en) * 2006-10-09 2008-04-16 中国矿业大学(北京) A method for preparing schistose nanometer magnesium hydroxide and sphericity nanometer white carbon black using zillerite gangue
CN101323452A (en) * 2007-06-11 2008-12-17 肖莹 Method for preparing precipitated silica with boron sludge
CN102030349A (en) * 2010-11-29 2011-04-27 沈阳工业大学 Method for extracting magnesium hydroxide by using boric sludge and treating dye wastewater

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103923379A (en) * 2013-01-14 2014-07-16 中国地质大学(北京) Method for preparing fire retardation polymer composite material by using boron mud
CN103923379B (en) * 2013-01-14 2016-08-10 中国地质大学(北京) A kind of utilize boric sludge for the method for flame-retardant high-molecular composite
CN104446598A (en) * 2014-06-30 2015-03-25 中国地质大学(北京) Flame-retarding heat-insulating material based on boric sludgeand preparation method of flame-retarding heat-insulating material
CN104446598B (en) * 2014-06-30 2016-09-07 中国地质大学(北京) A kind of fire-retardant fireproof insulation material based on boron mud and preparation method thereof
CN104671262A (en) * 2015-01-30 2015-06-03 李广凡 Light magnesium carbonate prepared by boric sludge acidification method as well as production method and application thereof
CN104671262B (en) * 2015-01-30 2017-11-03 吴细霞 Light magnesium carbonate and its production method and purposes made from a kind of boron mud acidization
CN112316910A (en) * 2020-10-28 2021-02-05 东北大学 Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group
CN112316910B (en) * 2020-10-28 2021-11-05 东北大学 Method for preparing adsorbent by graft modification of waste boric sludge sulfonic acid group
CN112574504A (en) * 2020-11-20 2021-03-30 应急管理部沈阳消防研究所 Aerogel prepared by boron mud waste, flame retardant and modification application of aerogel
CN116282096A (en) * 2023-05-12 2023-06-23 中科镁基(北京)科技有限公司 Comprehensive utilization method of boric sludge

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Application publication date: 20121212