CN103130250A - Method for preparing active magnesium oxide - Google Patents
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- CN103130250A CN103130250A CN2011103728500A CN201110372850A CN103130250A CN 103130250 A CN103130250 A CN 103130250A CN 2011103728500 A CN2011103728500 A CN 2011103728500A CN 201110372850 A CN201110372850 A CN 201110372850A CN 103130250 A CN103130250 A CN 103130250A
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Abstract
A method for preparing active magnesium oxide comprises the following steps: injecting a raw material of a magnesium chloride solution, and mixed gas of NH3 and CO2 into a hypergravity reactor, performing a rapid mixing reaction of the gas and the liquid under a hypergravity condition, wherein the magnesium chloride solution concentration is 0.2-0.5 mol/L, the volume ratio of NH3 to CO2 is (1.6-2.4):1, the reaction temperature is 70-80 DEG C, the hypergravity level is 150-960 g, performing reaction precipitation, filtration, washing, and drying to obtain an intermediate of basic magnesium carbonate, then calcining the basic magnesium carbonate at a temperature of 500-900 DEG C to obtain the active magnesium oxide. The invention can reach the requirement of rapid gas-liquid mixing so as to realize rapid microscopic uniform mixing under a condition with a high reaction solution solute concentration and a large processing capacity, and thus reach the homogeneous nucleation condition required by the preparation of the intermediate of basic magnesium carbonate; the method of the invention is simple in process, easy to control, free of aging, high in efficiency, and high in product activity.
Description
Technical field
The present invention relates to a kind of preparation method of activated magnesia, specifically adopt gas-liquid short mix reaction precipitation to prepare the presoma magnesium basic carbonate, then at high temperature calcine the presoma magnesium basic carbonate and obtain activated magnesia, belong to the ultra-fine grain preparation field.
Background technology
Activated magnesia (Magnesium oxide, activated), molecular formula MgO, relative molecular mass 40.30,2852 ℃ of fusing points, boiling point is 3600 ℃, is a kind of odorless, tasteless, the nontoxic unformed powder of white.Activated magnesia is insoluble in water, is insoluble to alcohol, is dissolved in acid or ammonium salt solution.Solubleness in water is along with CO in water
2the increase of content and increasing.Absorb airborne carbonic acid gas and water and can generate magnesium basic carbonate.
Activated magnesia, due to the granular with particle, high reactivity, advantages such as photopermeability that specific surface area is large, good, is widely used in the fields such as electronics, electrical equipment, optics, instrument, national defence, aerospace.Activated magnesia can also be as efficient Dissociative agent, and the absorption toxic chemical substance, be widely used in field of environment protection.
The production method of activated magnesia is a lot, by the source difference of raw material, can be divided into: the one, and the production method that the mineral of take are raw material; The 2nd, the production method that the bittern of take is raw material.
(1) take the production method that mineral are raw material
Producing activated magnesia in traditional industry mainly take rhombspar and produces as raw material.The rhombspar main component is CaMg (CO
3)
2, chemical composition is CaO:41%, MgO:21.86%, CO
2: 47.33%.Belonging to trigonal system, is the double salt of calcium carbonate and magnesiumcarbonate.Its major impurity is Fe, and Mn also has Zn, Ni and Co once in a while.
Rhombspar carborization reaction principle is as follows:
MgCO
3·CaCO
3→MgO+CaO+2CO
2↑
MgO+CaO+2H
2O→Mg(OH)
2+Ca(OH)
2
Ca(OH)
2+2CO
2→CaCO
3+H
2O
Mg(OH)
2+2CO
2→Mg(HCO
3)
2
Mg(HCO
3)
2+2H
2O→MgCO
3·3H
2O+CO
2↑
5MgCO
3·3H
2O→4MgCO
3·Mg(OH)
2·8H
2O+6H
2O+CO
2↑
4MgCO
3·Mg(OH)
2·8H
2O→4MgCO
3·Mg(OH)
2·5H
2O+3H
2O
4MgCO
3·Mg(OH)
2·5H
2O→4MgCO
3·Mg(OH)
2·4H
2O+H
2O
4MgCO
3·Mg(OH)
2·4H
2O→5MgO+5H
2O+4CO
2↑
Its concrete chemical process, for rhombspar and anthracite proportioning are by a certain percentage sent into to calcining in the lime calcining cellar for storing things, obtains clinker dolomite (MgOCaO).In digestive shelf, directly clinker dolomite is digested to the dolomite ash breast with hot water or useless magnesium water under stirring state, again that certain density dolomite ash is newborn with being pumped into carbonating tower, use the carbonic acid gas through washing and purifying from lime calcining kiln to carry out carburizing reagent to Dolomite milk.The main component of the carbonization solution after carburizing reagent is Magnesium hydrogen carbonate, and throw out is calcium carbonate.Filter the heavy magnesium water that obtains clarification by flame filter press, through being pumped into the pyrolysis groove, with steam direct heating, make its pyrolysis generate magnesium basic carbonate clear liquor.Magnesium basic carbonate suspension liquid after pyrolysis filters and obtains filter cake through plate-and-frame filter press, and filter cake is predrying, and the remove portion free water, then deliver in calcining furnace, and calcining at a certain temperature obtains Product Activity magnesium oxide.
(2) take the production method that bittern is raw material
Producing high-purity and ultra-pure magnesium products with liquid magnesium resources such as seawater, bittern has many good qualities.The impurity phase contained in seawater, bittern is to less, simpler than removal of impurities in magnesium ore deposit as the impurity removing operation, and the cost of removal of impurities also can reduce greatly.Its preparation method mainly contains bittern carborization, bittern-ammonia process, bittern-ammonium carbonate method etc.
Bittern-carborization
This method is that to take the magnesium chloride containing solution such as bittern, seawater and Adlerika etc. be raw material, with the carbonic acid gas produced after rhombspar or limestone calcination, rhombspar or lime be raw material, digested, the reaction such as precipitation, carbonization, pyrolysis, calcining produces activated magnesia.
Bittern-carborization reaction principle is as follows:
Dolomite calcination MgCO
3caCO
3→ MgOCaO+2CO
2↑
Or limestone calcination CaCO
3→ CaO+2CO
2↑
Digestion MgOCaO+2H
2o → Mg (OH)
2+ Ca (OH)
2
Precipitation MgCl
2+ Ca (OH)
2→ Mg (OH)
2+ CaCl
2
Carbonization Mg (OH)
2+ 2CO
2→ Mg (HCO
3)
2
Pyrolysis Mg (HCO
3)
2+ 2H
2o → MgCO
33H
2o+CO
2↑
5MgCO
3·3H
2O→4MgCO
3·Mg(OH)
2·8H
2O+6H
2O+CO
2↑
4MgCO
3·Mg(OH)
2·8H
2O→4MgCO
3·Mg(OH)
2·5H
2O+3H
2O
4MgCO
3·Mg(OH)
2·5H
2O→4MgCO
3·Mg(OH)
2·4H
2O+H
2O
Calcining 4MgCO
3mg (OH)
24H
2o → 5MgO+5H
2o+4CO
2↑
The concrete reaction process of this method mainly comprises: rhombspar or Wingdale obtain dolomite ash through calcining, after adding water digestion, with bittern, react and obtain magnesium hydrate precipitate.Precipitated magnesium hydroxide obtains carbonization solution after carbonization, and its main component is Magnesium hydrogen carbonate.By clear liquor, through being pumped into the pyrolysis groove, pyrolysis generates magnesium basic carbonate.After the filtration of magnesium basic carbonate suspension liquid, washing, dehydration, drying and calcining after pyrolysis, obtain Product Activity magnesium oxide.
Bittern-ammonia process
The method is one of important method of producing activated magnesia.It has history very remote, and along with the progress of needs and the equipment of social development, this method also progressively occupies a tiny space in the production of activated magnesia.The principle of this technique is very simple, is about to the exquisite bittern of crossing and reacts the generation magnesium hydroxide with ammoniacal liquor, calcines and obtain Product Activity magnesium oxide.
The reaction principle of bittern-ammonia process is as follows:
MgCl
2+2NH
3·H
2O→Mg(OH)
2+2NH
4Cl
Mg(OH)
2→MgO+H
2O
Its main process comprises: the dry and calcining of the purification of bittern, logical ammonia precipitation magnesium hydroxide, magnesium hydroxide.Ammonia or ammoniacal liquor are passed in the exquisite bittern that concentration is 0.2mol/L, and temperature of reaction is advisable at 50-60 ℃, now Mg
2+transformation efficiency larger, pH value is greater than 12, is conducive to reaction and carries out to generating the magnesium hydrate precipitate direction, in order to obtain the magnesium hydroxide that particle is less, can adopt logical ammonia speed faster, generally in 1-2h, logical ammonia is complete.The reaction paste obtained is filtered and obtains magnesium hydrate precipitate by vacuum filter or plate-and-frame filter press.To precipitate repetitive scrubbing several times, wash away the soluble impurity that the magnesium hydroxide surface adsorption, obtain the magnesium hydroxide that purity is high.The magnesium hydrate precipitate washed is dewatered, dry, calcining obtains activated magnesia.
Bittern-ammonium carbonate method
The main raw material of this explained hereafter is bittern (or Magnesium dichloride hexahydrate) and volatile salt (or bicarbonate of ammonia) cheap and easy to get.
The reaction principle of bittern-ammonium carbonate method is as follows:
MgCl
2+4NH
4HCO
3+2H
2O→MgCO
3·(NH
4)
2CO
3·4H
2O+2NH
4Cl+2CO
2↑
5[MgCO
3·(NH
4)
2CO
3·4H
2O]→4MgCO
3·Mg(OH)
2·4H
2O+10NH
3+6CO
2↑+20H
2O
4MgCO
3·Mg(OH)
2·4H
2O→5MgO+5H
2O+4CO
2↑
Concrete technology is: by bittern purifying, be mixed with certain density strong solution, concentration and the bittern concentration of volatile salt are suitable.Volatile salt is joined in bittern, quickly heats up to more than 70 ℃ with superheated vapour, obtain a large amount of white precipitates, after system ageing 1h, put into suction filter, with deionized water wash to filtrate substantially without till chlorion.The filter cake obtained is transferred to drying in moisture eliminator, then pulverize, finally send in calcining furnace and calcine, obtain Product Activity magnesium oxide.
The shortcomings such as it is low that aforesaid method all exists purity, active low, and economy is low, and environmental benefit is low.The present invention compares with bittern-ammonium carbonate method and additive method, it is advantageous that, the standby Product Activity magnesium oxide of this legal system is not only active high but also purity is also very high, and this method does not need to prepare ammonium bicarbonate solution, the useless NH that can directly be discharged by factory
3and CO
2through hypergravity machine by MgCl
2make the precursor magnesium basic carbonate after solution coupling absorption reaction.Adopt hypergravity machine as reaction unit, use MgCl
2the solution coupling absorbs NH
3and CO
2prepare activated magnesia, both can save installation cost, can strengthen NH again
3and CO
2assimilation effect.And this technique is simple easily to be controlled, and preparation process does not need ageing, and the direct filtration drying and calcining obtains Product Activity magnesium oxide.
Summary of the invention
The present invention is directed to the deficiency that prior art exists, the production method of the activated magnesia that a kind of technique is simple, product yield is high, production cost is low, contamination-free produces is provided.
A kind of method for preparing activated magnesia of the present invention, is characterized in that, comprises the following steps: with industrial hex-ammoniate, CO
2and NH
3for raw material, take supergravity reactor as reaction unit, NH
3and CO
2volume ratio be (1.6-2.4): 1; At first, magnesium chloride solution is heated to 50-80 ℃, introduce rotor internal cavity by liquid inlet tube, through shower nozzle, be sprayed on the inner edge of rotating rotor, liquid enters after rotor the effect that is subject to filler in rotor, circumferential speed increases, and the centrifugal force of generation pushes it against the rotor outer rim, and liquid is thrown to shell by rotor and collects by liquid outlet tube and leave hypergravity machine; Carbonic acid gas, ammonia gas mixture through gas inlet tube by tangential introducing rotor exocoel, entering filler by the rotor outer rim under the effect of pressure difference contacts with liquid countercurrent, complete mass transfer and reaction process under the hypergravity condition after, gas leaves rotor from rotor center, by gas outlet tube, is drawn.The liquid circulation charging, the disposable charging of gas, whole reactive system is by the temperature regulating device temperature control, temperature of reaction keeps 70-80 ℃, reaction is filtered after finishing, the gained solid washes away ammonium ion and chlorion with deionized water, and under temperature 100-110 ℃, drying obtains the intermediates magnesium basic carbonate, subsequently magnesium basic carbonate is calcined and is obtained activated magnesia under temperature 500-900 ℃.Mother liquor send soda factory to recycle.Its reaction equation is as follows:
5MgCl
2+4CO
2+10NH
3+10H
2O→4MgCO
3·Mg(OH)
2·4H
2O+10NH
4Cl
4MgCO
3·Mg(OH)
2·4H
2O→5MgO+5H
2O+4CO
2↑
Density of magnesium chloride is 0.1-1mol/L, more preferably 0.2-0.5mol/L; Working pressure is normal pressure, 1atm; The preferred 150-960g of hypergravity level; The preferred 1-8 of vapour-liquid volume ratio; Calcining temperature remains on 500-900 ℃ of scope, preferably 500-700 ℃; The circulating reaction time is preferably 25-35min.
The reacted reaction mixture body of magnesium chloride solution and mixed gas counter current contact enters stirring tank through discharge gate, then through recycle pump, squeezes into supergravity reactor and continues to loop NH
3and CO
2absorption reaction, whole reactive system, by the temperature regulating device temperature control, filters after reaction reaches terminal, in temperature, is 100-110 ℃ of lower dry cake, obtain the intermediates magnesium basic carbonate, subsequently magnesium basic carbonate is calcined and obtained activated magnesia under temperature 500-900 ℃ condition.
Magnesium chloride solution of the present invention is configured according to common collocation method, and raw material adopts industrial hex-ammoniate, and dissolve medium adopts tap water.NH
3and CO
2can directly adopt the useless NH discharged by factory
3and CO
2.
Reaction raw materials density of magnesium chloride of the present invention is in certain limit, and density of magnesium chloride is low, though the product pattern is even, output is lower, and economic benefit is poor; If excessive concentration, cause reaching the condition of homogeneous nucleation before finishing inductive phase, can't obtain the uniform magnesium basic carbonate intermediate of pattern, the product reunion degree made is comparatively serious, and equipment easily stops up.Reaction raw materials density of magnesium chloride of the present invention is 0.1-1mol/L, preferably 0.2-0.5mol/L.
Temperature of reaction of the present invention keeps 70-80 ℃.If temperature of reaction is low, products therefrom is generally the mixture of magnesiumcarbonate double salt, its less stable; Temperature of reaction is too high, not easy to operate.
Supergravity reactor of the present invention is disclosed hypergravity swinging bed device, comprise the rotating packed bed reactor (application reference number 91109255.2,91111028.3,01268009.5,200520100685.3,02114174.6 and 200510032296.6) of the forms such as bed of packings, deflector type, helical channel, preferably hypergravity is rotary packed bed.
Hypergravity level of the present invention refers to the size of the centrifugal acceleration that hypergravity swinging bed device rotor rotation produces, and usually with the multiple of gravity acceleration g, means, the rotating speed of main and rotor and the internal-and external diameter of rotor are relevant.The horizontal g of hypergravity
rcan mean with following formula:
In formula: the rotating speed that n is the rotor per minute
R
1, r
2be respectively the inside and outside footpath of rotor
Hypergravity level of the present invention is controlled at certain limit according to the needs of preparation, completes the full and uniform mixing of magnesium chloride solution and mixed gas to guarantee decomposition induction time before finishing, thereby meets the needed homogeneous nucleation condition of magnesium basic carbonate for preparing.The hypergravity level is too low, and it is insufficient that reactant mixes, and, after the hypergravity level acquires a certain degree, the raising of hypergravity level is on almost not impact of reaction.General experimental result is: higher at the wide-ultra gravity horizontal limited, will within the shorter time, reach required homogeneous nucleation condition, and the pattern of the intermediate product magnesium basic carbonate obtained is even, thus the magnesian activity of product is higher.The preferred 150-960g of hypergravity level.
Calcining temperature of the present invention remains on 500-900 ℃ of scope, preferably 500-700 ℃.If calcining temperature is too low, although the magnesian activity of product is high, it is incomplete that the intermediate magnesium basic carbonate decomposes; Calcining temperature is too high, although the decomposition of intermediate magnesium basic carbonate is very thorough, the product MgO activity is low.
The operations such as separation of the present invention, filtration, washing, drying and calcining are conventional treatment process.
It is raw material that the present invention can adopt bittern and industrial gaseous waste, and Product Activity is high, production cost is low, and contamination-free produces, and production technique is simple.Product is spheroidal particle, and the surface of spheroidal particle is comprised of the nanometer sheet decussate texture, and the quality index of this product reaches the activated magnesia quality standard that GB is announced simultaneously.Be mainly used in the fields such as electronics, electrical equipment, optics, instrument, national defence, aerospace.In addition, can also be as efficient Dissociative agent, the absorption toxic chemical substance, be widely used in field of environment protection.
Magnesium oxide prepared by the present invention is activated magnesia, and the product chemical index meets HG/T2573-94 standard premium grads index, as shown in table 1.
Table 1 activated magnesia chemical industry standard HG/T2573-94 standard
Activated magnesia iodine absorption value prepared by the present invention is greater than 120mgI
2/ g MgO, citric acid activity value (CAA) is less than 15s, and the average apparent granularity is less than 3 μ m, and specific surface area is greater than 13m
2/ g (but measuring method reference of activated magnesia iodine absorption value, citric acid activity value, average apparent granularity and specific surface area " magnesium compound production and application " (Hu Qingfu compiles, Chemical Industry Press, 2004))
Beneficial effect of the present invention: the present invention is applied to the magnesium chloride solution coupling to high-gravity technology and absorbs NH
3and CO
2prepare the intermediate magnesium basic carbonate, then calcining obtains activated magnesia, utilize the characteristic of supergravity reactor strengthening microcosmic mixing and mass transfer, and control corresponding processing condition, and not only can reach the be beyond one's reach requirement of gas-liquid short mix of traditional reactor, make under the condition higher at the reaction soln solute concentration, that treatment capacity is large, can realize that quick microcosmic evenly mixes, reach and prepare the needed homogeneous nucleation condition of intermediate magnesium basic carbonate, and technique easily controls, without ageing.Method simple process of the present invention, efficiency is high, and Product Activity is high, and the scale that is easy to is amplified.
The accompanying drawing explanation
Fig. 1 is the schematic diagram of the technical process of the embodiment of the present invention;
(1) head tank, (2) pump, (3) liquid meter, (4) supergravity reactor, (5,6,7) under meter, (8) gas mixing tank, (9) gas meter, (10) liquid distributor, (11) temperature regulating device;
Fig. 2 is the stereoscan photograph of the prepared activated magnesia of the present invention;
(a), (b) corresponding embodiment 1, (c), (d) corresponding embodiment 2, (e), (f) corresponding embodiment 3, (g), (h) corresponding embodiment 4.
Embodiment
Following examples just illustrate of the present invention, and the present invention is not limited to following examples.
Following examples all adopt the rhythmic reaction operating method, that is: certain density magnesium chloride solution is heated to assigned temperature in head tank, squeeze into supergravity reactor through recycle pump, with carbonic acid gas, ammonia and nitrogen (or air, be equivalent to simulate industrial gaseous waste) the gas mixture counter current contact, hybrid reaction, the liquid circulation charging, the disposable charging of gas, reaction is filtered after finishing, wash away ammonium ion and chlorion with deionized water, in temperature, be 100-110 ℃ of drying, obtain the intermediates magnesium basic carbonate, subsequently magnesium basic carbonate is calcined and is obtained under assigned temperature activated magnesia, its flow process is shown in Fig. 1.
To be heated to assigned temperature 50-80 ℃ in head tank (1) by certain density magnesium chloride solution, be squeezed in supergravity reactor (4) N by pump (2) through liquid meter (3)
2(or air, its purpose is in order to simulate industrial gaseous waste), NH
3, CO
2after gas mixing tank (8) mixes, by gas meter (9), be delivered to supergravity reactor through under meter (5,6,7).After starting reactor, magnesium chloride solution is introduced rotor internal cavity by liquid inlet tube, through liquid distributor (10), be sprayed on the inner edge of rotor, liquid enters after rotor the effect that is subject to filler in rotor, circumferential speed increases, under the effect of centrifugal force, by inner edge, to outer rim, flowed, pass into gas after system stability, gas mixture through gas inlet tube by tangential introducing, entering filler by the rotor outer rim under the effect of pressure reduction contacts with liquid countercurrent, the reaction mixture body enters stirring tank through discharge gate, then through recycle pump, squeezes into supergravity reactor and carries out NH
3and CO
2the circulation absorption reaction, whole reactive system, by temperature regulating device (11) temperature control, filters after reaction reaches terminal, in temperature, is 100-110 ℃ of lower dry cake, obtain the intermediates magnesium basic carbonate, subsequently magnesium basic carbonate lower calcining under 500-700 ℃ of condition is obtained to activated magnesia.
The preferred hypergravity of rotating bed super gravity reactor of the present invention is rotary packed bed, and the filler in packing layer includes, but are not limited to: the silk screen of metallic substance and non-metallic material, porous plate, waved plate, foam materials or structured packing.The hypergravity level of supergravity reactor is 150-960g, and the circulating reaction time is 25-35min.
Embodiment 1
The magnesium chloride solution 3L that compound concentration is 0.2mol/L, 70 ℃ of temperature of reaction, regulate liquid flow rate 100L/h, gas flow 350L/h, NH
3and CO
2volume content be respectively 22% and 13%, normal atmosphere of working pressure, rotating speed 600rpm, rotor diameter 15cm, internal diameter 5cm (the horizontal 220g of hypergravity), after reaction reaches terminal, vacuum filtration, with the deionized water washing leaching cake for several times, dry 10h at 100-110 ℃, obtain the intermediate magnesium basic carbonate, in temperature, be magnesium basic carbonate 700 ℃ of calcining 2h subsequently, product is that the surperficial bar-shaped activated magnesia be comprised of nanometer sheet (nanometer sheet is comprised of Nano microsphere) decussate texture is (as Fig. 2 (a), (b) shown in), particle length is respectively 10-15 μ m, width is all 2.5 μ m, nanometer sheet thickness 25nm left and right, the iodine absorption value of product is 110mgI
2/ g MgO, citric acid activity value (CAA value) is 11s, specific surface area 49m
2/ g, the utilization ratio of magnesium ion is 95%.
Embodiment 2
The magnesium chloride solution 3L that compound concentration is 0.3mol/L, 75 ℃ of temperature of reaction, regulate liquid flow rate 100L/h, gas flow 350L/h, NH
3and CO
2volume content be respectively 22% and 12%, normal atmosphere of working pressure, rotating speed 800rpm, rotor diameter 15cm, internal diameter 5cm (the horizontal 391g of hypergravity), after reaction reaches terminal, vacuum filtration, with the deionized water washing leaching cake for several times, dry 10h at 100-110 ℃, obtain the intermediate magnesium basic carbonate, in temperature, be magnesium basic carbonate 650 ℃ of calcining 2h subsequently, product is that the surperficial bar-shaped activated magnesia be comprised of the nanometer sheet decussate texture is (as Fig. 2 (c), (d) shown in), particle length is respectively 12-17 μ m, width is all 3 μ m, nanometer sheet thickness 20nm left and right, the iodine absorption value of product is 120mgI
2/ g MgO, citric acid activity value (CAA value) is 10s, specific surface area 56m
2/ g, the utilization ratio of magnesium ion is 97%.
Embodiment 3
The magnesium chloride solution 3L that compound concentration is 0.4mol/L, 80 ℃ of temperature of reaction, regulate liquid flow rate 100L/h, gas flow 350L/h, NH
3and CO
2volume content be respectively 22% and 11%, normal atmosphere of working pressure, rotating speed 1000rpm, rotor diameter 15cm, internal diameter 5cm (the horizontal 612g of hypergravity), after reaction reaches terminal, vacuum filtration, with the deionized water washing leaching cake for several times, dry 10h at 100-110 ℃, obtain the intermediate magnesium basic carbonate, in temperature, be magnesium basic carbonate 500 ℃ of calcining 2h subsequently, product is that the surperficial spherical activated magnesia be comprised of the nanometer sheet decussate texture is (as Fig. 2 (e), (f) shown in), the mean diameter of particle is 3 μ m, nanometer sheet thickness 20nm left and right, the iodine absorption value of product is 170mgI
2/ g MgO, citric acid activity value (CAA value) is 7s, specific surface area 97m
2/ g, the utilization ratio of magnesium ion is 96%.
The magnesium chloride solution 3L that compound concentration is 0.5mol/L, 73 ℃ of temperature of reaction, regulate liquid flow rate 100L/h, gas flow 350L/h, NH
3and CO
2volume content be respectively 22% and 10%, normal atmosphere of working pressure, rotating speed 1200rpm, rotor diameter 15cm, internal diameter 5cm (the horizontal 882g of hypergravity), after reaction reaches terminal, vacuum filtration, with the deionized water washing leaching cake for several times, dry 10h at 100-110 ℃, obtain the intermediate magnesium basic carbonate, in temperature, be magnesium basic carbonate 600 ℃ of calcining 2h subsequently, product is that the spherical activated magnesia that is comprised of the nanometer sheet decussate texture of surface is (as Fig. 2 (g), (h) shown in shown in), the mean diameter of particle is 2.5 μ m, nanometer sheet thickness 20nm left and right, the iodine absorption value of product is 150mgI
2/ g MgO, citric acid activity value (CAA value) is 8s, specific surface area 83m
2/ g, the utilization ratio of magnesium ion is 94%.
Claims (8)
1. a method for preparing activated magnesia, is characterized in that, comprises the following steps: with industrial hex-ammoniate, CO
2and NH
3for raw material, take supergravity reactor as reaction unit, NH
3and CO
2volume ratio be (1.6-2.4): 1; At first, magnesium chloride solution is heated to 50-80 ℃, be incorporated into the supergravity reactor rotor internal cavity by liquid inlet tube, through shower nozzle, be sprayed on the inner edge of rotor, liquid enters after rotor the effect that is subject to filler in rotor, circumferential speed increases, and the centrifugal force of generation pushes it against the rotor outer rim, and liquid is thrown to shell by rotor and collects by liquid outlet tube and leave hypergravity machine; Carbonic acid gas, ammonia gas mixture through gas inlet tube by tangential introducing rotor exocoel, entering filler by the rotor outer rim under the effect of pressure difference contacts with liquid countercurrent, complete mass transfer and reaction process under the hypergravity condition after, gas leaves rotor from rotor center, by gas outlet tube, is drawn; The liquid circulation charging, the disposable charging of gas, whole reactive system is by the temperature regulating device temperature control, temperature of reaction keeps 70-80 ℃, reaction is filtered after finishing, the gained solid washes away ammonium ion and chlorion with deionized water, and under temperature 100-110 ℃, drying obtains the intermediates magnesium basic carbonate, subsequently magnesium basic carbonate is calcined and is obtained activated magnesia under temperature 500-900 ℃; Above-mentioned density of magnesium chloride is 0.1-1mol/L, and working pressure is normal pressure.
2. method according to claim 1, is characterized in that, the hypergravity level of supergravity reactor is 150-960g.
3. method according to claim 1, is characterized in that, the vapour-liquid volume ratio is 1-8.
4. method according to claim 1, is characterized in that, density of magnesium chloride is 0.2-0.5mol/L.
5. method according to claim 1, is characterized in that, calcining temperature remains on 500-700 ℃.
6. method according to claim 1, is characterized in that, density of magnesium chloride is 0.2-0.5mol/L, the horizontal 150-960g of the hypergravity of supergravity reactor, vapour-liquid volume ratio 1-8; Calcining temperature remains on 500-700 ℃.
7. method according to claim 1, is characterized in that, circulating reaction time 25-35min.
8. according to the described either method of claim 1-7, it is characterized in that NH
3and CO
2for the useless NH directly discharged by factory
3with useless CO
2.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108733A (en) * | 2014-07-07 | 2014-10-22 | 新疆大正过程环保科技有限公司 | High-purity magnesia wet-pyrogenic integrated device and method for preparing high-purity magnesia |
| CN104445297A (en) * | 2014-11-03 | 2015-03-25 | 苏州市泽镁新材料科技有限公司 | Preparation method of nanometer magnesia |
| CN105936513A (en) * | 2016-06-02 | 2016-09-14 | 中国科学院青海盐湖研究所 | Basic magnesium carbonate and preparation method thereof |
| CN106517621A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Process of recycling wastewater containing ammonia chloride |
| CN106517294A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Method for preparing metal oxide |
| CN108439440A (en) * | 2018-06-05 | 2018-08-24 | 张勤福 | The technique for producing magnesia using peridotite ore |
| CN110182832A (en) * | 2019-05-25 | 2019-08-30 | 邢台镁熙环保材料有限公司 | A kind of petroleum catalyst special magnesium oxide production technology |
| CN110451537A (en) * | 2019-09-03 | 2019-11-15 | 淄博美盛化工有限公司 | The device of magnesium chloride producing magnesium oxide by carbonization method and its prepare method of magnesium oxide |
| CN111017967A (en) * | 2019-12-27 | 2020-04-17 | 河北镁神科技股份有限公司 | Green, environment-friendly and clean production process of ultra-pure magnesium oxide |
| CN111634929A (en) * | 2020-05-08 | 2020-09-08 | 中国科学院青海盐湖研究所 | Method for preparing active magnesium oxide from magnesium slag and method for preparing magnesium cement |
| CN111661858A (en) * | 2020-06-24 | 2020-09-15 | 上海宝鼎机械制造有限公司 | Silicon steel grade magnesium oxide and preparation method thereof |
| CN113952917A (en) * | 2021-10-18 | 2022-01-21 | 济源市鲁泰纳米材料有限公司 | Hypergravity reactor and preparation method of active nano zinc oxide prepared by same |
| CN114180603A (en) * | 2020-12-11 | 2022-03-15 | 安徽金禾实业股份有限公司 | Method for producing active magnesium oxide from waste residues of spices |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108733B (en) * | 2014-07-07 | 2015-12-09 | 新疆大正过程环保科技有限公司 | Highly-purity magnesite wets fire one subtraction unit and prepare the method for highly-purity magnesite |
| CN104108733A (en) * | 2014-07-07 | 2014-10-22 | 新疆大正过程环保科技有限公司 | High-purity magnesia wet-pyrogenic integrated device and method for preparing high-purity magnesia |
| CN104445297A (en) * | 2014-11-03 | 2015-03-25 | 苏州市泽镁新材料科技有限公司 | Preparation method of nanometer magnesia |
| CN106517294B (en) * | 2015-09-09 | 2021-02-26 | 有研稀土新材料股份有限公司 | Process for producing metal oxide |
| CN106517621A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Process of recycling wastewater containing ammonia chloride |
| CN106517294A (en) * | 2015-09-09 | 2017-03-22 | 有研稀土新材料股份有限公司 | Method for preparing metal oxide |
| CN106517621B (en) * | 2015-09-09 | 2021-08-10 | 有研稀土新材料股份有限公司 | Recycling process of ammonium chloride-containing wastewater |
| CN105936513A (en) * | 2016-06-02 | 2016-09-14 | 中国科学院青海盐湖研究所 | Basic magnesium carbonate and preparation method thereof |
| CN105936513B (en) * | 2016-06-02 | 2017-10-31 | 中国科学院青海盐湖研究所 | A kind of basic magnesium carbonate and preparation method thereof |
| CN108439440A (en) * | 2018-06-05 | 2018-08-24 | 张勤福 | The technique for producing magnesia using peridotite ore |
| CN110182832A (en) * | 2019-05-25 | 2019-08-30 | 邢台镁熙环保材料有限公司 | A kind of petroleum catalyst special magnesium oxide production technology |
| CN110451537A (en) * | 2019-09-03 | 2019-11-15 | 淄博美盛化工有限公司 | The device of magnesium chloride producing magnesium oxide by carbonization method and its prepare method of magnesium oxide |
| CN111017967A (en) * | 2019-12-27 | 2020-04-17 | 河北镁神科技股份有限公司 | Green, environment-friendly and clean production process of ultra-pure magnesium oxide |
| CN111634929A (en) * | 2020-05-08 | 2020-09-08 | 中国科学院青海盐湖研究所 | Method for preparing active magnesium oxide from magnesium slag and method for preparing magnesium cement |
| CN111661858A (en) * | 2020-06-24 | 2020-09-15 | 上海宝鼎机械制造有限公司 | Silicon steel grade magnesium oxide and preparation method thereof |
| CN114180603A (en) * | 2020-12-11 | 2022-03-15 | 安徽金禾实业股份有限公司 | Method for producing active magnesium oxide from waste residues of spices |
| CN113952917A (en) * | 2021-10-18 | 2022-01-21 | 济源市鲁泰纳米材料有限公司 | Hypergravity reactor and preparation method of active nano zinc oxide prepared by same |
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