CN101941723B - Method for producing high-activity nano magnesia by utilizing low-grade magnesite - Google Patents

Method for producing high-activity nano magnesia by utilizing low-grade magnesite Download PDF

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CN101941723B
CN101941723B CN2010102750470A CN201010275047A CN101941723B CN 101941723 B CN101941723 B CN 101941723B CN 2010102750470 A CN2010102750470 A CN 2010102750470A CN 201010275047 A CN201010275047 A CN 201010275047A CN 101941723 B CN101941723 B CN 101941723B
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magnesium
magnesia
magnesite
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CN101941723A (en
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王国胜
宁志高
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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Abstract

The invention relates to a method for producing high-activity nano magnesia by utilizing low-grade magnesite, in particular to a method for producing nano magnesite. The method utilizes a chemical reaction principle and comprises the following steps of: firstly, roasting low-grade magnesite or powdered ore to obtain magnesia, reacting the magnesia and sulphuric acid and filtering to obtain a magnesium sulfate solution; purifying the solution by adopting a neutralizer and an oxidant to obtain a purified magnesium sulfate solution; adding ammonium bicarbonate and a surfactant to the purified magnesium sulfate solution and roasting to obtain high-activity nano magnesia; heating and decomposing the ammonium sulfate contained filtrate obtained in the last step and light burning powder to obtain magnesium hydroxide at a flame retardant level; and filtering the magnesium hydroxide in a reactor to obtain magnesium hydroxide at an environmental protection level and recycling the filtrate without emission. Fibrous magnesium hydroxide, basic magnesium carbonate and high-activity nano magnesia are widely applied to flame retardance, smoke suppression, filling and reinforcement of rubber products, can be used as an adiabatic and high-temperature-resistant insulation material or can be used for manufacturing high-grade glass products, magnesium salts, paints, and the like.

Description

Utilize low-grade magnesite to produce the method for high reactivity, nano magnesia
Technical field
The present invention relates to a kind of method of producing nano magnesia, particularly relate to a kind of method of utilizing low-grade magnesite to produce high reactivity, nano magnesia.
Background technology
At present, during Chinese magnesite uses, exist high-quality magnesite overexploitation is used, and the problem that low-grade magnesite or fine ore, mine tailing are failed to make full use of.Cause the recovering plant cover of mine problem serious, the comprehensive utilization of resources degree is not high.Not only range of product is few, and product specification is not high yet.
Utilize the chemical industry technical characterstic, to low-grade magnesite, particularly, significant for being that development of raw materials is produced magnesium chemical products through the light burnt powder (content of magnesia is between 65%-80%) that obtains after calcining with low-grade (or powdery) magnesite.
Classification utilizes principle according to giobertite, changes raw material property product, and the general layout of products production of low grade is utilized low grade material, produces high-grade, functionalization Magnesium Chemical Materials like flame-proof magnesium hydroxide, magnesium basic carbonate; Meticulous specific function Magnesium Chemical Materials such as high reactivity, nano level Natural manganese dioxide.Added value of product is high, and is good in economic efficiency, and the advantage of performance chemical industry technology makes great efforts to accomplish energy-saving and emission-reduction, and when making full use of resource, the protection environment makes the production symbol of Magnesium Chemical Materials and the requirement of Sustainable development.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing low-grade magnesite to produce high reactivity, nano magnesia; The product of producing with this method has difunctionally, has high reactivity and nano level performance simultaneously; Quality is high, added value is high; Consider in technological process that simultaneously waste liquid can reclaim utilization again, this method reaction process zero release can produce environment protection and double benefit economically.
The objective of the invention is to realize through following technical scheme:
Utilize low-grade magnesite to produce the method for high reactivity, nano magnesia; Present method is utilized chemical principle; At first with low-grade magnesite or powdered ore, through obtaining content of magnesia light burnt powder between 65%-80% after the calcining; Obtain Adlerika with sulfuric acid reaction, after filtering, adopt neutralizing agent and oxygenant that solution purification is handled, remove foreign ion; Adlerika after being purified, a part adds bicarbonate of ammonia and tensio-active agent, produces magnesium basic carbonate, obtains high-activity nano Natural manganese dioxide after the calcining; Another part, the filtrating and the light burnt powder thermal degradation of the sulfur acid ammonium that was obtained by the last step feed the ammonia that steams, and obtain the Marinco H of flame retardant grade, obtain environmental protection level Marinco H behind the reactor drum inner filtration, and filtrate recycle does not have discharging, gets final product.
Advantage of the present invention and effect are:
1. present method has proposed a kind of preparation high-activity nano Natural manganese dioxide working method, and product has difunctional, has high reactivity and nano level performance simultaneously, and quality is high, and added value is high.
2. the light burnt powder (content of magnesia is between 65%-80%) that obtains after adopting low-grade (or powdery) magnesite through calcining is a raw material; With the unavailable raw material of refractory materials; Utilize the chemical industry technology to make full use of low-grade magnesite resource, help the magnesite resource comprehensive utilization.
3. considered that waste liquid is recycled in the technological process, obtained being applicable to fire-retardant and Marinco H environmental protection that realization technology does not have discharging.
Description of drawings
Accompanying drawing 1 is high reactivity, nano magnesia technological process of production skeleton diagram.
Embodiment
The present invention adopts low-grade (or powdery), and magnesite is raw material through the light burnt powder (content of magnesia is between 65%-80%) that obtains after calcining; Adopt sulfuric acid process to obtain Adlerika; After the removal of impurities, obtain heavy magnesium water, add tensio-active agent with the bicarbonate of ammonia metathesis; Pyrolytic reaction obtains magnesium basic carbonate, obtains high reactivity, nano level Natural manganese dioxide after the calcining.The filtrating of the sulfur acid ammonium that filtration is obtained and light burnt powder reaction, the ammonia that steams are reacted with Adlerika and are obtained Marinco H, obtain environmental protection level Marinco H behind the reactor drum inner filtration, filtrate recycle.Fibrous Marinco H, magnesium basic carbonate and high-activity nano Natural manganese dioxide be widely used in rubber item fire-retardant, press down cigarette, filling and reinforcement; Can be used as thermal insulation, high-temperature-resistant thermal-insulation material; Also can be used to make high glass goods, magnesium salts, paint etc.
With reference to the accompanying drawings the present invention is elaborated.
1. ultimate principle of the present invention
(1) it is following that the magnesia unslacked that obtains of magnesite calcining carries out the reaction formula of acidolysis removal of impurities process:
MgO+H 2SO 4→MgSO 4+H 2O (1)
CaO+H 2SO 4→CaSO 4↓+H 2O (2)
FeO+H 2SO 4→FeSO 4+H 2O (3)
Fe 2O 3+3H 2SO 4→Fe 2(SO 4) 3+H 2O (4)
Al 2O 3+3H 2SO 4→Al 2(SO 4) 3+H 2O (5)
Figure BSA00000260553800031
(2) magnesia unslacked that obtains of magnesite fine ore or mine tailing calcining carries out ammonium and soaks with the reaction formula of acidolysis removal of impurities process following:
Figure BSA00000260553800032
Figure BSA00000260553800033
Figure BSA00000260553800034
Figure BSA00000260553800035
MgO+H 2SO 4→MgSO 4+H 2O (11)
Figure BSA00000260553800036
(3) removing impurities by oxidation:
2Fe 2++2H ++H 2O 2→Fe 3++2H 2O (13)
Fe 3++3NH 3·H 2O→Fe(OH) 3↓+3NH + 4 (14)
Al 3++3NH 3·H 2O→Al(OH) 3↓+3NH + 4 (15)
(4) replacement(metathesis)reaction obtains heavy magnesium water solution
MgSO 4+2NH 4HCO 3→Mg(HCO 3) 2+(NH 4) 2SO 4 (16)
(5) pyrolysis obtains magnesium basic carbonate
Figure BSA00000260553800041
(6) the ammonia method is produced flame-proof magnesium hydroxide
Figure BSA00000260553800042
(7) calcining obtains high-activity nano level Natural manganese dioxide
2. general planning of the present invention
The first step, the magnesia unslacked that magnesite calcining is obtained carries out acidolysis and removal of impurities, and the magnesia unslacked that magnesite fine ore or mine tailing calcining are obtained carries out the acidolysis removal of impurities;
Second step neutralized and oxidation to the solution after the removal of impurities, continued to remove the foreign metal ion;
In the 3rd step, the solution after the removal of impurities is carried out replacement(metathesis)reaction obtain heavy magnesium water solution;
In the 4th step, the pyrolysis of the counterweight magnesium aqueous solution obtains medicine food level magnesium basic carbonate, and the counterweight magnesium aqueous solution carries out ammonification and obtains flame-proof magnesium hydroxide;
In the 5th step, calcining obtains high-activity nano level Natural manganese dioxide to magnesium basic carbonate.
3. technological method of the present invention
The light burnt powder (content of magnesia is between 65%-80%) that the present invention obtains after adopting acid hydrolyzation processing low-grade (or powdery) magnesite through calcining, method is simple, and is easy to operate.Pay attention to recycling research in the technological process, realized recycle, improved raw material availability, reduced production cost emission gases and waste liquid.
4. the concrete embodiment of the present invention
Get the light burnt powder (content of magnesia is between 65%-80%) of 100g, add the dilute sulphuric acid that 120ml water and 60～120ml vitriol oil are made into, be heated to 75 ℃, reaction 2h, filtered while hot is removed insolubles, obtains thick Adlerika 1.
Measure thick Adlerika 200ml solution, heat to 45 ℃～50 ℃, add the MgO reaction of 3～5g several times in the solution, stirring reaction 5 minutes drips the ydrogen peroxide 50 of 4ml, produces reddish-brown precipitation, filters and obtains containing MgSO 4Filtrating do not contain other impurity basically.
Press mass ratio 3/1 (NH 4HCO 3/ MgSO 4), add NH in the sal epsom filtrating after purifying 4HCO 3(40 ℃ of temperature) generates heavy magnesium water solution, adds the OP emulsifying agent of 3% (mass ratio of OP emulsifying agent and Magnesium hydrogen carbonate). and the pyrolytic reaction of positive magnesiumcarbonate then takes place in temperature in the time of 70 ℃～105 ℃, generate magnesium basic carbonate; The filter residue that obtains after the product of reaction filters is magnesium basic carbonate, and sending into retort furnace after to its washing and drying carries out high temperature (600～900 ℃) calcining 2 hours, generates high reactivity, nano magnesia.
Iodine absorption value: (gI 2/ gMgO) between 120～190.
Natural manganese dioxide particle diameter: median size: 25nm.
Get the light burnt powder (content of magnesia is between 65%-80%) of 200g; With the filtrating of the sulfur acid ammonium of 300ml, in reactor drum, dissolve, add excessive ammonium sulfate 120g; Reacting by heating under 90 ℃ of conditions; The ammonia of emitting feeds and is in another reactor drum that the Adlerika 600ml after the purification is arranged, and recycles, and obtains fibrous Marinco H behind the sedimentation and filtration.
No longer include when steaming ammonia, stop heating, deposition obtains environmental protection level Marinco H after the filtration.The reuse in the lump of filtrating.

Claims (1)

1. utilize low-grade magnesite to produce the method for high reactivity, nano magnesia, it is characterized in that: low-grade magnesite obtains content of magnesia light burnt powder between 65%-80% after calcining;
Get the light burnt powder of 100g, add the dilute sulphuric acid that 120ml water and 60～120ml vitriol oil are made into, be heated to 75 ℃, reaction 2h, filtered while hot is removed insolubles, obtains thick Adlerika;
Measure thick Adlerika 200ml solution, heat to 45 ℃～50 ℃, add the MgO reaction of 3～5g several times in the solution, stirring reaction 5 minutes drips the ydrogen peroxide 50 of 4ml, produces reddish-brown precipitation, filters and obtains containing MgSO 4Filtrating do not contain other impurity basically;
Press NH 4HCO 3/ MgSO 4Mass ratio 3/1 adds NH in the sal epsom filtrating after purifying 4HCO 3, 40 ℃ of temperature generate heavy magnesium water solution, add the OP emulsifying agent of Magnesium hydrogen carbonate quality 3%, and the pyrolytic reaction of positive magnesiumcarbonate then takes place in temperature in the time of 70 ℃～105 ℃, generate magnesium basic carbonate; The filter residue that obtains after the product of reaction filters is magnesium basic carbonate, and sending into retort furnace after to its washing and drying carries out 600～900 ℃ of high-temperature calcinations 2 hours, generates high reactivity, nano magnesia;
Iodine absorption value: gI 2/ gMgO is between 120～190;
Natural manganese dioxide particle diameter: median size: 25nm.
CN2010102750470A 2010-09-08 2010-09-08 Method for producing high-activity nano magnesia by utilizing low-grade magnesite Expired - Fee Related CN101941723B (en)

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CN102392303B (en) * 2011-11-29 2013-11-06 沈阳化工大学 Method for preparing basic magnesium chloride whisker from light-burnt powder with one-step process
CN102976369B (en) * 2012-11-12 2014-11-12 沈阳化工大学 Method for preparing ultrafine magnesium hydroxide and basic magnesium sulfate whiskers from low-grade magnesite
CN103803592B (en) * 2014-01-26 2015-12-30 乌鲁木齐金石徽龙矿业有限公司 A kind of two fire grates that adopt burn the technique of legal system for high-purity magnesium oxide
CN104843748A (en) * 2014-02-14 2015-08-19 中国科学院过程工程研究所 Low-grade magnesite and low-grade magnesite tailing comprehensive recycling use method
CN107298451B (en) * 2017-06-12 2018-12-18 沈阳化工大学 A kind of low-grade magnesite magnesium carbon is double to utilize method
CN107417146B (en) * 2017-07-18 2019-07-05 沈阳化工大学 A kind of low-grade magnesite method of comprehensive utilization
CN109942010A (en) * 2019-05-07 2019-06-28 辽宁科技大学 A method of light calcined magnesia is purified using nitrate
CN111422891A (en) * 2020-05-14 2020-07-17 沈阳工业大学 Method for comprehensive utilization of magnesite
CN112320826A (en) * 2020-10-29 2021-02-05 刘峰 Method for jointly preparing high-purity magnesium oxide and refined ammonium sulfate by using low-grade magnesite
CN113104871B (en) * 2021-04-25 2022-07-26 北京化工大学 Method for preparing magnalium hydrotalcite from magnesite
CN113184883A (en) * 2021-05-11 2021-07-30 青海施丹弗化工有限责任公司 Method for continuously producing nano magnesium oxide

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