CN1887709A - Prepn process of magnesia for silicon steel - Google Patents
Prepn process of magnesia for silicon steel Download PDFInfo
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- CN1887709A CN1887709A CN 200610012973 CN200610012973A CN1887709A CN 1887709 A CN1887709 A CN 1887709A CN 200610012973 CN200610012973 CN 200610012973 CN 200610012973 A CN200610012973 A CN 200610012973A CN 1887709 A CN1887709 A CN 1887709A
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Abstract
The present invention relates to preparation process of magnesium compound, and is especially preparation process of magnesia for silicon steel. The present invention produces silicon steel level magnesia through a bittern-sodium carbonate process, which includes reaction of refined magnesium chloride solution and refined sodium carbonate solution at 65-85 deg.c for 5-15 min to produce basic magnesium carbonate, curing, filtering and calcining at 1100+/-50 deg.c for 2.0+/-0.5 hr. Thus produced silicon steel level magnesia has high purity, small average grain size, good coating performance, high adhesivity and other features, and the preparation process is simple and low in cost.
Description
Technical field
The present invention relates to a kind of preparation method of magnesium compound, be specially a kind of preparation process of magnesia for silicon steel that is exclusively used in the oriented silicon steel sheet.
Background technology
As everyone knows, silicon steel level magnesium oxide is white powder, and is nonpoisonous and tasteless, be exclusively used in the manufacturing of oriented silicon steel sheet, and the oriented silicon steel sheet mainly is used as the iron core of range transformer.In the manufacturing processed of oriented silicon steel sheet, silicon steel level magnesium oxide is the high temperature annealing separant between the siliconized plate, can form fine and close good Magnesium Silicate q-agent insulating film layer with siliconized plate surface, and can remove impurity such as sulphur in the siliconized plate, phosphorus, reduce the iron loss of siliconized plate, improve electrical property etc.Silicon steel level magnesium oxide belongs to high-tech product, and at present the whole world can produce less than 6 families of the magnesian producer of silicon steel level, and nearly 10000 tons of ultimate production, and nearly 1600000 tons of global demand amounts are so supply falls short of demand in market.Making the magnesian production technique of silicon steel level at present mainly contains: bittern-ammonification carbon method, rhombspar-carborization, bittern-ammoniacal liquor method, bittern-ammonium carbonate method, bittern-lime method etc., but, there is following defective in these preparation methods: 1, the technological process of production is longer, wayward stable product quality the more important thing is that to cause cost higher; 2, the silicon steel level magnesium oxide chemical purity of preparing is low, impurity is high, in application, exist viscosity little and poor, the granularity of coating tack is big and physicals such as irrational distribution on defective, thereby directly influence the quality of Magnesium Silicate q-agent insulating film layer, do not reach industry requirement far away.
Summary of the invention
Existing preparation process of magnesia for silicon steel technical process is long in order to solve, the chemical purity of the finished product is low and defective such as physicals difference and a kind of preparation process of magnesia for silicon steel is provided in the present invention.
The present invention adopts following technical scheme to realize: preparation process of magnesia for silicon steel comprises following processing step:
(1) adding volume in reactor is that V1, volumetric molar concentration are the purified magnesium chloride solution of 1.5 ± 0.5mol/L, under the 500-1000r/min whipped state, speed adding volume with 80-150L/min is that V2, volumetric molar concentration are the prepared calcium carbonate sodium solution of 1.5 ± 0.5mol/L, reaction times is 5-15min, V1: V2=1.1-1.2 wherein: 1.0, temperature of reaction maintains 65-85 ℃, finally generates magnesium basic carbonate, sodium-chlor and water;
(2) add water and to make solid-to-liquid ratio be 1 in above-mentioned resultant: 30-50 is 10-40r/min in stir speed (S.S.) then, and the time is 2.5 ± 0.5h, and temperature is 65-85 ℃ of following slaking;
(3) be 1 with the magnesium basic carbonate after the above-mentioned slaking at 65-85 ℃, solid-to-liquid ratio: filter under the condition of 10-25, the water content of controlling magnesium basic carbonate simultaneously is 65-80%;
(4) magnesium basic carbonate after will filtering is 1100 ± 50 ℃ in temperature, and constant temperature time is to carry out the static state calcining under 2.0 ± 0.5h, can get magnesium oxide;
(5) adopt the comminution by gas stream mode that magnesium oxide is carried out particle size separation, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.
Optimised process step of the present invention is as follows: adding volume in reactor is V1, volumetric molar concentration is the purified magnesium chloride solution of 1.5 ± 0.2mol/L, under the 600-800r/min whipped state, speed adding volume with 100-120L/min is V2, volumetric molar concentration is the prepared calcium carbonate sodium solution of 1.5 ± 0.2mol/L, reaction times is 5-10min, V1: V2=1.05-1.1 wherein: 1.0, temperature of reaction maintains 70-75 ℃, the final magnesium basic carbonate that generates, sodium-chlor and water, adding water and make solid-to-liquid ratio in above-mentioned resultant is 1: 40, be 20-30r/min in stir speed (S.S.) then, time is 1-2h, temperature is 70-75 ℃ of following slaking, with the magnesium basic carbonate after the above-mentioned slaking at 75-80 ℃, solid-to-liquid ratio is to filter under 1: 20 the condition, the water content of controlling magnesium basic carbonate simultaneously is 70-75%, is 1100 ± 20 ℃ with the magnesium basic carbonate after filtering in temperature, constant temperature time is to carry out the static state calcining under 2.0 ± 0.5h, can get magnesium oxide, adopt fluidized bed jet mill that magnesium oxide is carried out particle size separation then, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.
Purified magnesium chloride solution of the present invention is that bittern is diluted with water to concentration is 1.5 ± 0.5mol/L, it is 50-60 ℃ that heating makes its temperature, under whipped state, add the oxygenant clorox then, its add-on is 3% of a magnesium chloride, add 0.2% soda ash then, stir 30min, filtration gets final product; And the prepared calcium carbonate sodium solution is that soda ash is dissolved in the water, and being diluted to concentration is 1.5 ± 0.5mol/L, and heating makes its temperature get final product at 50-60 ℃.
Of the present inventionly reacted resultant is added water cure and filtering processing step can suitably increase according to production technique with to the performance requriements of the finished product, the present invention adopts two maturation, twice filtration, like this can be with the Cl in the magnesium basic carbonate, Na
+, SO
4 2-Thoroughly remove Deng detrimental impurity.
Magnesian preparation raw material of silicon steel level of the present invention and reaction mechanism are as follows:
1, raw material:
Magnesium chloride is commonly called as bittern, molecular formula MgCl
26H
2O, molecular weight 203.31
Yellow soda ash is commonly called as soda ash, molecular formula NaCO
3, molecular weight 105.99
2, reaction mechanism:
React under certain condition with bittern (magnesium chloride) and soda ash (yellow soda ash) and to make magnesium basic carbonate, then with magnesium basic carbonate through handling, the silicon steel of calcining manufacturing under certain condition level magnesium oxide.Its chemical equation is as follows:
Bittern of the present invention-soda ash method is produced being analyzed as follows of magnesian concrete processing step of silicon steel level and processing parameter:
1, the pre-treatment of raw material:
A. the technical grade magnesium chloride generally all contains some deleterious impurity, as Fe
2+, Mn
2+, water-insoluble etc.Bittern is diluted with water to concentration at 1.5 ± 0.2mol/L, and heating makes its temperature at 50-60 ℃, adds oxygenant-clorox (NaClO) under whipped state, its dosage is 3% of a magnesium chloride dosage, add 0.2% yellow soda ash then, stir 30min, make the Fe in the magnesium chloride
2+Be oxidized to Fe
3+, generate Fe (OH)
3Precipitation, Mn
2+Be oxidized to Mn
4+, generate MnO
2Precipitation.Its ionic reaction formula is as follows:
B. soda ash is dissolved in the water, being diluted to concentration is 1.5 ± 0.2mol/L, and heating makes its temperature at 50-60 ℃, promptly gets the prepared calcium carbonate sodium solution.
Magnesium chloride and sodium carbonate solution are filtered to remove main deleterious Fe (OH)
3, MnO
2, solid phase impurity such as water-insoluble, make clarifying purified magnesium chloride solution and prepared calcium carbonate sodium solution.
2, reaction process: reaction formula is as follows:
Adding volume in glass-lined reactor is the purified magnesium chloride solution of V1, under the 500-1000r/min whipped state, speed with 80-150L/min adds the prepared calcium carbonate sodium solution V2 more excessive than magnesium chloride, reaction times is 5-15min, V1: V2=1.1-1.2 wherein: 1.0, temperature of reaction maintains 65-85 ℃, and the magnesium basic carbonate crystalline form that makes thus trends towards the spheric amorphous powder.
Processing condition are analyzed:
A: temperature of reaction: the temperature of reaction height directly influences quality product.Learn that through overtesting temperature of reaction is lower than 65 ℃, be difficult to generate spherical magnesium basic carbonate, mobile poor, look specific volume greater than 4.0ml/g; If temperature greater than 85 ℃, is looked specific volume less than 3.0ml/g, for after magnesium oxide granularity and aquation rate all produce unfavorablely, so temperature of reaction is controlled at 65-85 ℃, the best is 70-75 ℃.
B: churning time and stirring velocity: in synthetic precipitin reaction system, the stirring velocity size is to guarantee to produce to be tending towards one of spherical magnesian important factor.Stirring velocity is big, the reaction system homogeneous, but spheroidal crystal is destroyed; Stirring velocity is little, and reaction system is inhomogeneous.Show that through production test stirring velocity is 500-1000r/min, the best is 600-800r/min.Churning time is long also can to influence products production speed and shape of product; Churning time is too short, and its crystal growth is incomplete, and test shows that after having added sodium carbonate solution, the system reaction times is 5-15min, and the best is 5-10min.
C: yellow soda ash adds speed: this bittern-soda ash method reaction system is the moment reaction in theory, in order to obtain the product than homogeneous, must add speed by strict control yellow soda ash.Test shows that too fast when adding, speed of response is accelerated, but reaction system is inhomogeneous, is difficult to form spherical product; Adding speed is slow excessively, and prolong reaction time, and throughput descends.In order to guarantee product spherical form and look the specific volume claimed range to greatest extent, can increase productivity again, selecting yellow soda ash adding speed is 80-150L/min, the best is 100-120L/min.
D: the equimolar ratio of magnesium chloride and yellow soda ash: this chemosynthesis is both reaction with same mole.Show that in production practice excessive when magnesium chloride, its finished product filter and washing easily, otherwise opposite.If yellow soda ash is excessive, the system pH value increases, and causes filter cloth to harden, stop up easily, thereby filtration velocity is descended, thus adopt magnesium chloride more excessive than yellow soda ash, V1: V2=1.1-1.2: 1.0, optimum proportion is V1: V2=1.05-1.1: 1.0.
In reaction, magnesium chloride solution volume V1 and soda ash solution volume V2 summation must not be above 2/3 of volumes in the reactor, in order to avoid reaction solution is overflowed by vessel port.
3, initial slaking: the initially slaking of magnesium basic carbonate that reaction obtains, carry out the transition to stable magnesium basic carbonate by the meta magnesium basic carbonate, in addition for guaranteeing that crystal grows up, reach certain particle size, maturing process will slowly stir, and speed is 20-30r/min, and the time is 1.0-2.0h, PH=9.5-10.3, temperature is 45-75 ℃.
4, once filter: the magnesium basic carbonate of preparing is a turbid solution, and temperature is 25-40 ℃ of filtration.Industrial employing link-suspended basket centrifuge separates solid-liquid.Solid exists with magnesium basic carbonate, and liquid mainly is to exist with sodium chloride solution.In order to obtain the sodium chloride solution of peak concentration, this process does not adopt deionized water wash, and the water content of only controlling magnesium basic carbonate gets final product at 75-85%.
5, post cure: also contain a spot of Cl, Na in the above-mentioned magnesium basic carbonate of producing
+, SO
4 2-Etc. deleterious impurity solubility ion, and magnesium basic carbonate crystal grain heterogeneity, so need be with this filter cake at curing in water 2.5 ± 0.5h, temperature is 65-85 ℃, solid-to-liquid ratio is 1: 30-50 (amounting to butt magnesium oxide weight meter).Maturing process will slowly stir, and speed is 10-40r/min.In this process, small-particle continues to grow up, be adsorbed, in the mixed crystal, water content with foreign ion replaced.
6, secondary filtration: the magnesium basic carbonate of above-mentioned slaking in 65-85 ℃ of following filtered while hot, and is washed with water, and solid-to-liquid ratio is 1: 10-25 (amounting to butt magnesium oxide weight meter), at this moment, soluble ion Cl, Na
+, SO
4 2-Get rid of Deng effectively, only contain the extremely foreign ion of trace in the solids, controlling moisture content is between 65-80%.Because this moment, crystal grain became big, thus water content during than inceptive filtering water content low.
7, calcining: magnesium basic carbonate is sloughed carbonic acid gas in the magnesiumcarbonate and the water molecules in the magnesium hydroxide, and its chemical equation is as follows:
Calcination condition is to the micromorphologic influence of product: too high magnesian secondary agglomeration and the final sintering of causing easily of temperature, and product grains is grown up, surface-area descends, the active reduction; Temperature is low excessively, and product master content descends, and calcination loss strengthens, and the aquation rate strengthens, active increasing.Promote heat-up rate when magnesia calcined, product is decomposed being higher than under its decomposition temperature, crystal dissociates soon.So it is 1100 ± 50 ℃ that the present invention adopts calcining temperature, the best is 1100 ± 20 ℃, and constant temperature time is 2.0 ± 0.5h, and static calcining in continuous tunnel furnace.Static calcining can make the granularity of product, crystalline form not be destroyed, and can improve the product production rate.If adopt the rotary kiln calcining, then tiny granularity product will be fled from gas air inducing in the magnesium oxide, cause the product production rate to descend.
8, pulverize (coarse crushing): magnesium oxide is after calcining, and airtight cooling can reduce aquation rate content.Generally be cooled to 30-50 ℃, get final product coarse crushing.
Magnesium oxide produces caking phenomenon owing to be subjected to high-temperature calcination, its particle to have part to reunite.Mechanical crusher is selected in coarse crushing for use, and particle generally reaches the 100 particle size separation work that just can change next step now over to.At this moment, controlled oxidation magnesium looks specific volume at 3.0-4.0ml/g.If look specific volume greater than 4.0ml/g, product is active after follow-up airflow milling increases, and vaporization rate increases; And be lower than 3.0ml/g, and magnesium oxide is active to be reduced, and product granularity increases.
9, particle size separation (secondary pulverizing): the magnesium oxide after the coarse crushing is carried out two grade pulverization, in 320 orders, screenings≤0.5%, D50≤2.5um.The present invention utilizes fluidized bed jet mill to carry out two grade pulverization, if necessary, can handle and control the granularity of product by grading machine.Fluidized bed jet mill is an intense impact of utilizing high velocity air, material is collided mutually and reaches the purpose of pulverizing.High pressure gas divide two-way to enter pulverizer, lead up to behind in a row, the paired nozzle, become at a high speed or ultrasonic jet, are ejected into and pulverize the district; Another road enters from feeder, material is ejected into pulverizes the district, material is collided mutually, rubbing makes the material pulverizing in the eddy current that is formed by jet.The advantage in air-flow geomantic omen is that product can not polluted, and product granularity is little.
10, mix: in order to regulate product activity, it being controlled in the 5S, is that those of ordinary skill in the art is known.
11, packing: though silicon steel level magnesium oxide aquation rate is low than industrial magnesium oxide, place air can absorb moisture and carbonic acid gas for a long time, generate magnesium hydroxide or further generate magnesium basic carbonate, so mould in needing to adopt 2 layers or 6 layers of kraft paper packing.Experimental observation detects, quality guaranteed period≤9 month.
The present invention has done following optimization Test to the important technology parameter in the processing step:
(1) volumetric molar concentration in magnesium chloride and yellow soda ash when reaction is to the influence of product granularity and foreign matter content:
Select for use the volumetric molar concentration of magnesium chloride, yellow soda ash to be respectively 0.5mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L, synthetic by previous reaction technology, its influence to granularity (representing with D50) and impurity ion content (representing with Cl) is as shown in the table:
| Volumetric molar concentration, mol/L | Granularity (D50) um | Foreign ion (Cl), % |
| 0.5 | 0.4 | 0.003 |
| 1.0 | 0.6 | 0.006 |
| 1.5 | 1.1 | 0.01 |
| 2.0 | 1.8 | 0.04 |
| 2.5 | 2.6 | 0.10 |
Can find out that from last table when feed molar concentration is big more, granularity is big more, foreign ion is many more; Volumetric molar concentration is more little, and granularity is more little, and foreign ion is also more little.When volumetric molar concentration during less than 1.0mol/L, will cause water consumption obviously to increase, and can obviously observe and escape to expect that phenomenon is serious, the product yield also reduces; When volumetric molar concentration during greater than 2.0mol/L, the foreign ion difficult treatment.So it is 1.5 ± 0.5mol/L that the present invention controls its volumetric molar concentration, the best is 1.5 ± 0.2mol/L.
(2) calcining temperature, time are to the influence of product viscosity and aquation rate:
Choose by the prepared magnesium basic carbonate of technology of the present invention in 1000 ℃, 1050 ℃, 1150 ℃, 1200 ℃ and calcine at identical time constant temperature 2.0h, the silicon steel level magnesium oxide that makes is as shown in the table to the influence of viscosity, aquation rate:
| Temperature, ℃ | Viscosity, CP | The aquation rate, % |
| 1000 | 80 | 5.6 |
| 1050 | 65 | 3.0 |
| 1100 | 60 | 2.4 |
| 1150 | 30 | 1.6 |
| 1200 | 18 | 1.2 |
Choose by the prepared magnesium basic carbonate of technology of the present invention in 1.0h, 1.5h, 2.0h, 3.0h, 4.0h, 5.0h and under 1100 ℃ condition, the silicon steel level magnesium oxide that makes is as shown in the table to the influence of viscosity and aquation rate:
| Time, h | Viscosity, CP | The aquation rate, % |
| 1.0 | 63 | 2.8 |
| 1.5 | 61 | 2.5 |
| 2.0 | 60 | 2.4 |
| 3.0 | 58 | 2.0 |
| 4.0 | 50 | 1.8 |
| 5.0 | 45 | 1.7 |
From above-mentioned two tables, find out, silicon steel level magnesium oxide in producing process to the susceptibility of temperature more than time-sensitive, mainly be reflected in viscosity and aquation rate.In certain hour, temperature is high more, and viscosity is more little, and the aquation rate is low more; At a certain temperature, the time is long more, and viscosity is more little, and the aquation rate is low more.The present invention is through overtesting, and taken all factors into consideration the performance index of product and the relation of production cost, and choosing calcining temperature is 1100 ℃ ± 50 ℃, and optimum temps is 1100 ℃ ± 20 ℃, and the calcining at constant temperature time is 2.0 ± 0.5h.
The silicon steel level magnesium oxide that is made by processing method of the present invention detects by East China country metrology and measurement center-Shanghai Institute of Measurement and Testing Technology; the detected result of gained is as shown in the table; its examining report sees Appendix 1; name is called the magnesian examining report of silicon steel level; and compare with the Shanghai product that Thailand and external Israel Dead Sea chemical industry company limited produced that shakes, the result is as follows:
| Technical indicator | The Thailand of shaking | The present invention | Israel |
| MgO(950℃，2.5h)％ | 98.2 | 99.1 | 98.6 |
| CaO，％ | 0.40 | 0.25 | 0.20 |
| Cl，％ | 0.03 | 0.01 | 0.03 |
| SO 4，％ | 0.33 | 0.10 | 0.20 |
| Fe，％ | 0.045 | 0.02 | 0.02 |
| Mn，％ | 0.003 | 0.001 | 0.002 |
| Calcination loss, % | 1.05 | 0.98 | 1.26 |
| Screenings (320 order), % | 1.1 | 0.05 | 0.05 |
| Viscosity, CP | 38 | 60 | 62 |
| The aquation rate, % | 2.2 | 2.4 | 3.6 |
| Viscosity D50, um | 3.2 | 1.1 | 1.2 |
| Look specific volume, ml/g | 4.5 | 4.2 | 4.8 |
| Foreign matter impurity | Meet | Meet | Meet |
Can find out obviously that from last table the magnesian every technical indicator of the silicon steel level that the present invention developed all is better than Shanghai shake Thailand and Israel Dead Sea chemical industry company limited, especially magnesian content all is higher than both.
In a word, the present invention compared with prior art, the silicon steel level magnesium oxide of being produced has the chemical purity height, foreign ion is low, median size is little and viscosity is high, characteristics such as coating, tack are good; Its physicals is much better than like product, and formed Magnesium Silicate q-agent insulating film layer quality is good, is the good annealing separating agent of producing the oriented silicon steel sheet; And production process is simple, cost is lower.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1:
It is 1.0mol/L that bittern is diluted with water to concentration, and it is 50 ℃ that heating makes its temperature, adds the oxygenant clorox then under whipped state, and its add-on is 3% of a magnesium chloride, adds 0.2% soda ash then, stirs 30min, filters and promptly gets purified magnesium chloride solution.Soda ash is dissolved in the water, and being diluted to concentration is 1.0mol/L, and heating makes its temperature promptly get the prepared calcium carbonate sodium solution at 50 ℃.Adding volume in reactor is that V1, volumetric molar concentration are the purified magnesium chloride solution of 1.0mol/L, under the 500r/min whipped state, speed adding volume with 800L/min is that V2, volumetric molar concentration are the prepared calcium carbonate sodium solution of 1.0mol/L, reaction times is 5min, V1: V2=1.10 wherein: 1.0, temperature of reaction maintains 65 ℃, finally generates magnesium basic carbonate, sodium-chlor and water; Be 20r/min in stir speed (S.S.) then, the time is 1.0h, PH=9.5, and temperature is to carry out initial slaking under 45 ℃ the condition, be cooled to 25 ℃ then and once filter, and the water content of magnesium basic carbonate is controlled at 75%.Adding water and make solid-to-liquid ratio in above-mentioned resultant is 1: 30, is 10r/min in stir speed (S.S.) then, and the time is 0.5h, and temperature is to carry out post cure under 65 ℃; Be to carry out secondary filtration under 1: 10 the condition at 65 ℃, solid-to-liquid ratio with the magnesium basic carbonate after the above-mentioned slaking, the water content of controlling magnesium basic carbonate simultaneously is 65%; Is 1050 ℃ with the magnesium basic carbonate after filtering in temperature, and constant temperature time is to carry out the static state calcining under the 1.5h, can get magnesium oxide; Adopt airflow milling that magnesium oxide is carried out particle size separation, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.Mix at last, pack, can sell.
Embodiment 2:
It is 2.0mol/L that bittern is diluted with water to concentration, and it is 60 ℃ that heating makes its temperature, adds the oxygenant clorox then under whipped state, and its add-on is 3% of a magnesium chloride, adds 0.2% soda ash then, stirs 30min, filters and promptly gets purified magnesium chloride solution.Soda ash is dissolved in the water, and being diluted to concentration is 2.0mol/L, and heating makes its temperature promptly get the prepared calcium carbonate sodium solution at 60 ℃.Adding volume in reactor is that V1, volumetric molar concentration are the purified magnesium chloride solution of 2.0mol/L, under the 1000r/min whipped state, speed adding volume with 150L/min is that V2, volumetric molar concentration are the prepared calcium carbonate sodium solution of 2.0mol/L, reaction times is 15min, V1: V2=1.2 wherein: 1.0, temperature of reaction maintains 85 ℃, finally generates magnesium basic carbonate, sodium-chlor and water; Be 30r/min in stir speed (S.S.) then, the time is 2.0h, PH=10.3, and temperature is to carry out initial slaking under 75 ℃ the condition, be cooled to 40 ℃ then and once filter, and the water content of magnesium basic carbonate is controlled at 85%.Adding water and make solid-to-liquid ratio in above-mentioned resultant is 1: 50, is 40r/min in stir speed (S.S.) then, and the time is 2.5h, and temperature is to carry out post cure under 85 ℃; Be to carry out secondary filtration under 1: 25 the condition at 85 ℃, solid-to-liquid ratio with the magnesium basic carbonate after the above-mentioned slaking, the water content of controlling magnesium basic carbonate simultaneously is 80%; Is 1150 ℃ with the magnesium basic carbonate after filtering in temperature, and constant temperature time is to carry out the static state calcining under the 2.5h, can get magnesium oxide; Adopt airflow milling that magnesium oxide is carried out particle size separation, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.Mix at last, pack, can sell.
Embodiment 3:
It is 1.3mol/L that bittern is diluted with water to concentration, and it is 40 ℃ that heating makes its temperature, adds the oxygenant clorox then under whipped state, and its add-on is 3% of a magnesium chloride, adds 0.2% soda ash then, stirs 30min, filters and promptly gets purified magnesium chloride solution.Soda ash is dissolved in the water, and being diluted to concentration is 1.3mol/L, and heating makes its temperature promptly get the prepared calcium carbonate sodium solution at 40 ℃.Adding volume in reactor is that V1, volumetric molar concentration are the purified magnesium chloride solution of 1.3mol/L, under the 600r/min whipped state, speed adding volume with 100L/min is that V2, volumetric molar concentration are the prepared calcium carbonate sodium solution of 1.3mol/L, reaction times is 10min, V1: V2=1.05 wherein: 1.0, temperature of reaction maintains 70 ℃, finally generates magnesium basic carbonate, sodium-chlor and water; Be 25r/min in stir speed (S.S.) then, the time is 1.5h, PH=10, and temperature is to carry out initial slaking under 50 ℃ the condition, be cooled to 30 ℃ then and once filter, and the water content of magnesium basic carbonate is controlled at 80%.Adding water and make solid-to-liquid ratio in above-mentioned resultant is 1: 40, is 20r/min in stir speed (S.S.) then, and the time is 1.0h, and temperature is to carry out post cure under 70 ℃; Be to carry out secondary filtration under 1: 20 the condition at 75 ℃, solid-to-liquid ratio with the magnesium basic carbonate after the above-mentioned slaking, the water content of controlling magnesium basic carbonate simultaneously is 70%; Is 1080 ℃ with the magnesium basic carbonate after filtering in temperature, and constant temperature time is to carry out the static state calcining under the 2.0h, can get magnesium oxide; Adopt airflow milling that magnesium oxide is carried out particle size separation, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.Mix at last, pack, can sell.
Embodiment 4:
It is 1.7mol/L that bittern is diluted with water to concentration, and it is 55 ℃ that heating makes its temperature, adds the oxygenant clorox then under whipped state, and its add-on is 3% of a magnesium chloride, adds 0.2% soda ash then, stirs 30min, filters and promptly gets purified magnesium chloride solution.Soda ash is dissolved in the water, and being diluted to concentration is 1.7mol/L, and heating makes its temperature promptly get the prepared calcium carbonate sodium solution at 55 ℃.Adding volume in reactor is that V1, volumetric molar concentration are the purified magnesium chloride solution of 1.7mol/L, under the 800r/min whipped state, speed adding volume with 120L/min is that V2, volumetric molar concentration are the prepared calcium carbonate sodium solution of 1.7mol/L, reaction times is 10min, V1: V2=1.1 wherein: 1.0, temperature of reaction maintains 75 ℃, finally generates magnesium basic carbonate, sodium-chlor and water; Be 30r/min in stir speed (S.S.) then, the time is 1.8h, PH=10.2, and temperature is to carry out initial slaking under 60 ℃ the condition, be cooled to 35 ℃ then and once filter, and the water content of magnesium basic carbonate is controlled at 80%.Adding water and make solid-to-liquid ratio in above-mentioned resultant is 1: 45, is 35r/min in stir speed (S.S.) then, and the time is 2.0h, and temperature is to carry out post cure under 75 ℃; Be to carry out secondary filtration under 1: 20 the condition at 80 ℃, solid-to-liquid ratio with the magnesium basic carbonate after the above-mentioned slaking, the water content of controlling magnesium basic carbonate simultaneously is 75%; Is 1120 ℃ with the magnesium basic carbonate after filtering in temperature, and constant temperature time is to carry out the static state calcining under the 2.5h, can get magnesium oxide; Adopt airflow milling that magnesium oxide is carried out particle size separation, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.Mix at last, pack, can sell.
Embodiment 5:
It is 1.5mol/L that bittern is diluted with water to concentration, and it is 50 ℃ that heating makes its temperature, adds the oxygenant clorox then under whipped state, and its add-on is 3% of a magnesium chloride, adds 0.2% soda ash then, stirs 30min, filters and promptly gets purified magnesium chloride solution; Soda ash is dissolved in the water, and being diluted to concentration is 1.5mol/L, and heating makes its temperature promptly get the prepared calcium carbonate sodium solution at 60 ℃.Adding volume in reactor is V1, volumetric molar concentration is the purified magnesium chloride solution of 1.5mol/L, under the 700r/min whipped state, speed adding volume with 110L/min is V2, volumetric molar concentration is the prepared calcium carbonate sodium solution of 1.5mol/L, reaction times is 8min, V1: V2=1.08 wherein: 1.0, temperature of reaction maintains 74 ℃, the final magnesium basic carbonate that generates, sodium-chlor and water, be 25r/min in stir speed (S.S.) then, time is 1.8h, PH=10.3, and temperature is to carry out initial slaking under 75 ℃ the condition, be cooled to 35 ℃ then and once filter, and the water content of magnesium basic carbonate is controlled at 80%.Adding water and make solid-to-liquid ratio in above-mentioned resultant is 1: 40, be 30r/min in stir speed (S.S.) then, time is 2h, temperature is to carry out post cure under 75 ℃, with the magnesium basic carbonate after the above-mentioned slaking at 75 ℃, solid-to-liquid ratio is to carry out secondary filtration under 1: 20 the condition, the water content of controlling magnesium basic carbonate simultaneously is 72%, is 1100 ℃ with the magnesium basic carbonate after filtering in temperature, constant temperature time is to carry out the static state calcining under the 2.0h, can get magnesium oxide, adopt fluidized bed jet mill that magnesium oxide is carried out particle size separation then, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.Mix at last, pack, can sell.
Claims (4)
1, a kind of preparation process of magnesia for silicon steel is characterized in that comprising following processing step:
(1) adding volume in reactor is that V1, volumetric molar concentration are the purified magnesium chloride solution of 1.5 ± 0.5mol/L, under the 500-1000r/min whipped state, speed adding volume with 80-150L/min is that V2, volumetric molar concentration are the prepared calcium carbonate sodium solution of 1.5 ± 0.5mol/L, reaction times is 5-15min, V1: V2=1.1-1.2 wherein: 1.0, temperature of reaction maintains 65-85 ℃, finally generates magnesium basic carbonate, sodium-chlor and water;
(2) add water and to make solid-to-liquid ratio be 1 in above-mentioned resultant: 30-50 is 10-40r/min in stir speed (S.S.) then, and the time is 0.5-2.5h, and temperature is 65-85 ℃ of following slaking;
(3) be 1 with the magnesium basic carbonate after the above-mentioned slaking at 65-85 ℃, solid-to-liquid ratio: filter under the condition of 10-25, the water content of controlling magnesium basic carbonate simultaneously is 65-80%;
(4) magnesium basic carbonate after will filtering is 1100 ± 50 ℃ in temperature, and constant temperature time is to carry out the static state calcining under 2.0 ± 0.5h, can get magnesium oxide;
(5) adopt the comminution by gas stream mode that magnesium oxide is carried out particle size separation, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.
2, preparation process of magnesia for silicon steel according to claim 1, it is characterized in that described optimised process step is as follows: adding volume in reactor is V1, volumetric molar concentration is the purified magnesium chloride solution of 1.5 ± 0.2mol/L, under the 600-800r/min whipped state, speed adding volume with 100-120L/min is V2, volumetric molar concentration is the prepared calcium carbonate sodium solution of 1.5 ± 0.2mol/L, reaction times is 5-10min, V1: V2=1.05-1.1 wherein: 1.0, temperature of reaction maintains 70-75 ℃, the final magnesium basic carbonate that generates, sodium-chlor and water, adding water and make solid-to-liquid ratio in the resultant of above-mentioned reaction is 1: 40, be 20-30r/min in stir speed (S.S.) then, time is 1-2h, temperature is 70-75 ℃ of following slaking, with the magnesium basic carbonate after the above-mentioned slaking at 75-80 ℃, solid-to-liquid ratio is to filter under 1: 20 the condition, the water content of controlling magnesium basic carbonate simultaneously is 70-75%, is 1100 ± 20 ℃ with the magnesium basic carbonate after filtering in temperature, constant temperature time is to carry out the static state calcining under 2.0 ± 0.5h, can get magnesium oxide, adopt fluidized bed jet mill that magnesium oxide is carried out particle size separation then, in 320 orders, screenings is less than or equal to 0.5%, and D50 is less than or equal to 2.5um.
3, preparation process of magnesia for silicon steel according to claim 1 and 2, it is characterized in that described purified magnesium chloride solution is that bittern is diluted with water to concentration is 1.5 ± 0.5mol/L, it is 50-60 ℃ that heating makes its temperature, under whipped state, add the oxygenant clorox then, its add-on is 3% of a magnesium chloride, add 0.2% soda ash then, stir 30min, filtration gets final product.
4, preparation process of magnesia for silicon steel according to claim 1 and 2, after it is characterized in that the reaction of described purified magnesium chloride solution and prepared calcium carbonate sodium solution, be 20-30r/min at first in stir speed (S.S.), time is 1.0-2.0h, PH=9.5-10.3, temperature is to carry out initial slaking under 45-75 ℃ the condition, be cooled to 25-40 ℃ then and once filter, and the water content of magnesium basic carbonate is controlled at 75-85%.
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Assignee: Heshun Yinsheng Chemical Co., Ltd. Assignor: Yinhai Magnesium Industry Co., Ltd., Heshun County Contract fulfillment period: 2008.3.16 to 2026.7.23 Contract record no.: 2009990001186 Denomination of invention: Prepn process of magnesia for silicon steel Granted publication date: 20080312 License type: Exclusive license Record date: 20091026 |
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Effective date of registration: 20210827 Address after: 032700 Room 101, first floor, Shanxi Yinsheng Technology Co., Ltd., North Binhe Road, Heshun County, Jinzhong City, Shanxi Province Patentee after: Shanxi Yinhai Fengyuan New Material Co.,Ltd. Address before: 032700 Shanxi province and County town of Pine Village pine Patentee before: Yinhai Magnesium Industry Co.,Ltd. Heshun County |