CN106986360A - The method that calcic magnesium carbonate thing ore deposit prepares magnesium hydroxide - Google Patents
The method that calcic magnesium carbonate thing ore deposit prepares magnesium hydroxide Download PDFInfo
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- CN106986360A CN106986360A CN201710214101.2A CN201710214101A CN106986360A CN 106986360 A CN106986360 A CN 106986360A CN 201710214101 A CN201710214101 A CN 201710214101A CN 106986360 A CN106986360 A CN 106986360A
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- magnesium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/16—Magnesium hydroxide by treating magnesia, e.g. calcined dolomite, with water or solutions of salts not containing magnesium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
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Abstract
The present invention provides a kind of method that calcium-magnesium-containing carbonate mine prepares magnesium hydroxide, comprises the following steps：（1）Ammonium sulfate solution carbonate mine is added into reactor, reactants separate obtains gas phase, liquid phase and solid phase；（2）The gas phase fractional condensaion of acquisition is obtained into ammonium bicarbonate solution；（3）The liquid phase of acquisition is added in water-soluble organic alkali solution, stirred, filtering obtains filter cake and filtrate；（4）Calcium hydroxide is added into step（3）Reacted in the filtrate of acquisition, reaction is filtered after terminating, and is obtained filter cake and filtrate, is regard at least a portion in filtrate as step（1）Raw material；（5）By step（2）Obtained ammonium bicarbonate solution and to step（4）Obtained filter cake, is reacted, filtering, is obtained filtrate, is regard at least a portion in filtrate as step（1）Raw material.Method of the present invention substantially increases the utilization rate of magnesium ion compared to more traditional ammonia-soda process synthesis magnesium hydroxide technique.
Description
Technical field
The invention belongs to chemical production technical field, and in particular to a kind of calcium-magnesium-containing carbonate mineral production magnesium hydroxide
Method.
Background technology
Magnesium hydroxide is a kind of important inorganic magnesium salt series of products, alkalescent is presented, while magnesium hydroxide reaches in temperature
Magnesia and water are resolved into during to 300~350 DEG C, then switchs to magnesia completely higher than 500 DEG C, the two characteristics cause hydroxide
The purposes of magnesium is quite varied, and such as industrial application magnesium hydroxide is as exhaust gas desulfurization absorbent, the hydrogen to instead preceding use
Sodium oxide molybdena and calcium hydroxide and for neutralizing acid waste water.The higher decomposition temperature of magnesium hydroxide and smokeless, nontoxic, cheap
Characteristic cause it to be also a kind of good fire retardant, particularly in synthetic resin manufacture field, previously used bromine system, phosphorus
The fire retardants such as system, chlorine system have that smoke amount is big, easily produce the big defects such as poisonous susceptibility-to-corrosion gas when fire-retardant, are also easy to produce
Secondary injury.And be all that the processing temperature of the aluminium hydroxide of inorganic fire-retardant agent only has about 200 DEG C or so, it is impossible to take into account very well
The higher resin of processing temperature.In addition to the main application direction of two above, magnesium hydroxide also has in field of medicaments sufficiently should
With.With gradually tightening up for Environmental Protection in China policy, a series of Green Products by representative of magnesium hydroxide are increasingly by people
Favor.
China's magnesium resource is compared with horn of plenty, and such as magnesite estimation gross reserves is about 3,000,000,000 tons, and dolomite reserves are about 4,000,000,000 tons,
And there is the abundant resource of lake bittern water containing magnesium salts in west area.But the domestic utilization for these magnesium resources at present is still located
In a kind of stage of extensive style, raw material availability is low, product specification and price are all relatively low, high-end fire retardant magnesium hydroxide, high-purity
The market demand of magnesium hydroxide and magnesia is big and mostly relies on import, and this also causes the research and development of high-end magnesium products to seem
It is particularly urgent.
Current magnesium hydroxide production technology can be divided into two classes, i.e. ore method and bittern method from raw material sources.Ore method is led to
Cross the magnesium formation magnesia or magnesium salts extracted in rich magnesium ore and then magnesium hydroxide is obtained by aquation or synthesis；And bittern
Rule be after handling magnesium-containing brine by synthesis obtain magnesium hydroxide.Magnesium-containing ore production magnesium salts is relied on typically to use
Process route be all that a certain degree of calcining is first carried out to ore or acidolysis, obtained magnesium oxide or magnesium salts is directly carried out
Aquation is carried out again or precipitation production magnesium hydroxide is carried out with ammonia alkali.Whole technological process is longer, for produce low cost, height
For the magnesium hydroxide of quality, the integrated optimization of exploitation and whole technological process to method is particularly important.
A kind of decomposition method for calcium carbonate and magnesium carbonate ore deposit that the patent of application number 201510881187.5 is provided, the invention is by drawing
Enter multi-stage countercurrent cascade reaction kettle or tower reactor, realize the reaction of ammonium salt decomposition calcium carbonate and magnesium carbonate ore deposit efficient stable, drop
Low energy consumption cost, it is economical.Any one of the calcium carbonate and magnesium carbonate miberal powder in agstone, magnesite powder, dolomite dust,
Ammonium salt is ammonium sulfate, ammonium chloride, ammonium nitrate.The ammonium bicarbonate solution that this method is steamed is used directly for producing magnesium carbonate, realizes thing
Material balance and comprehensive utilization.But this method is not suitable for producing magnesium hydroxide, comes because being decomposited when doing magnesium hydroxide products
CO2It can not be totally consumed, make material uneven and the conversion ratio with ammonia precipitation magnesium ion is limited, also to increase ammonia still process work
Sequence and energy consumption, increase production cost.
A kind of utilization magnesite production magnesium sulfate of Application No. 02130915.9 patent report, magnesium carbonate and magnesium hydroxide
Method, this method uses the light calcined magnesia that magnesite is calcined for raw material, add ammonium sulfate and the industrial concentrated sulfuric acid carry out it is sour molten
And ammonia still process, the magnesium sulfate then obtained using reaction and the ammonia precipitation process being collected into obtain magnesium hydroxide products.Unnecessary ammonia is used
Sulfuric acid absorption producing ammonium sulfate byproduct, ammonium bicarbonate soln and sulfuric acid reactive magnesium obtain carbonic acid magnesium products.Although the method achieve life
Production process closed cycle, no waste gas waste water is produced.But it is due to that ammonia process production magnesium hydroxide yield is not high, the sky of increase magnesium salts is followed
Ring, increases running cost, and magnesite is sintered into magnesia high energy consumption.
Application number 201110215664.6 reports a kind of method that utilization light dolomite prepares magnesium hydroxide, this method
Light dolomite, the concentrated sulfuric acid and slightly water-soluble organic amine are used for Material synthesis magnesium hydroxide, one of the process more protrudes
Advantage be slightly water-soluble organic amine split-phase reclaim have inexpensive and convenient advantage, but the technical process still suffer from it is several
Obvious defect, such as light dolomite need cost in higher calcining heat, energy consumption very high；Middle mistake is used as using the concentrated sulfuric acid
Cross simply this low surcharge of gypsum that raw material finally gives simultaneously and have the product of pollution to environment, it is economically uneconomical；
Slightly water-soluble organic amine causes the relatively low yield for causing magnesium ion of its pH value to be limited due to poorly water-soluble, and such magnesium ion is just
The waste that magnesium resource is caused inside gypsum can be entered.
The patent of application number 201110215665.0 is related to a kind of method that utilization sulfuric acid magnesium raw material prepares magnesium hydroxide, its profit
With precipitating reagent of the organic amine as magnesium ion, calcium oxide reclaims organic amine as basifier, recycles the water microsolubility of organic amine
Realize that aqueous amine is separated, make organic amine reusable edible, effectively reduce the use cost of organic amine.Although this method avoid ammonia
The problem of ammonia still process and ammonia volatilization are to the pollution of environment in method synthesis magnesium hydroxide technique, but be due to the poorly water-soluble of organic amine,
Can equally there is magnesium yield low, magnesium resource is wasted and by-product is low value-added and easily causes the calcium sulfate product of environmental pollution.Together
When in terms of whole technical process, due to lack such as evaporation water treatment process, cause system water constantly accumulation or
It is that the problem of system water is accumulated can only can be just prevented effectively from using the Adlerika even anhydrous magnesium sulfate of very high concentration,
But these measures are all economically irrational.
Application number 201110215701.3 provides a kind of method that theobromine dissolution magnesium ion raw material prepares magnesium hydroxide,
Magnesium hydroxide is made also with slightly water-soluble organic base and soluble magnesium salt reaction precipitation in the invention, is then reclaimed with calcium oxide
Organic base, calcium ion by-product calcium sulfate is separated with sulfuric acid.This method equally exists magnesium ion precipitation not exclusively, and magnesium ion only has
90% or so conversion ratio, remaining magnesium can enter byproduct calcium sulfate and lose；Introducing the concentrated sulfuric acid simultaneously can only finally obtain
It is equally also uneconomical to low value-added and with environmental pollution threat calcium sulfate product.
In summary, although the production method at present using rich magnesium ore as magnesium hydroxide is more and more ripe, particularly give birth to
The technique study of production high-performance magnesium hydroxide is also constantly lifted.But still there is high energy consumption, energy utilization not in most of technology
Fully, the low technical problem of magnesium ion utilization rate.And organic amine synthesizes the life of magnesium hydroxide as a kind of alkali in precipitation magnesium ion
Have prominent advantage on production. art, but be due to conventional research because of the organic amine poorly water-soluble of selection, cause magnesium ion to turn
Turn to magnesium hydroxide yield be limited, reclaim organic amine process in magnesium ion easily by plaster splint band, cause the wasting of resources and
Increase cost.So, research and development one kind prepares Gao Pin using rich magnesium ore as raw material with low energy consumption, economy, environmental protection, efficient method
The magnesium hydroxide of matter has a very big significance.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of preparation of calcium-magnesium-containing carbonate mine
The method of magnesium hydroxide, for solving deficiency of the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of calcium-magnesium-containing carbonate mine and prepares magnesium hydroxide
Method, at least comprise the following steps：
(1) ammonium sulfate solution and calcium-magnesium-containing carbonate mine are added into autoclave to be reacted, reaction product separation,
Obtain gas phase, liquid phase and solid phase；
Gas phase includes the mixed vapour of ammonia, carbon dioxide and water, and the solute of liquid phase includes magnesium sulfate, and solid phase includes sulfuric acid
Calcium；
Preferably, calcium-magnesium-containing carbonate mine is magnesite or dolomite mineral in the step (1), and the ammonium sulfate is dense
The mol ratio for spending the ammonium ion in 15~40wt%, the ammonium salt solution and calcium ions and magnesium ions in calcium-magnesium-containing carbonate mine is NH4 +：
(Ca2++Mg2+)=(3~2)：1.
Preferably, the reaction temperature is 140~220 DEG C, and reaction pressure is 0.4~2.5Mpa.
Preferably, the mixed vapour temperature is 140~220 DEG C, and pressure is 0.4~2.5Mpa.
(2) the gas phase fractional condensaion for obtaining step (1) obtains ammonium bicarbonate solution；
Fractional condensaion in the step (2) includes one-level and condensed and B-grade condensation, and the one-level condensation refers to step (1)
A gas phase part for middle acquisition as heating medium into the filtrate in one-level evaporator concentration and recovery step (5) or preferably,
The liquid phase of acquisition in step (1), while the indirect steam produced in evaporation process is used for into consolidating for the middle acquisition of baking step (1)
The filter cake mutually or in step (3) obtained；Another part gas phase in step (1) enters secondary condenser, for distilation steps
(5) thermal source of the filtrate obtained in.
Preferably, vinasse solution is obtained in the B-grade condensation is used for process water and cleaning magnesium hydroxide；Into
The vapor condensation of secondary condenser with calcium sulfate reaction into ammonium bicarbonate solution and for generating calcium carbonate.
The vinasse refers to that solution is distilled remaining water afterwards.
(3) liquid phase for obtaining step (1) is added in water-soluble organic alkali solution, is stirred, and is filtered, is obtained after reaction completely
To filter cake and filtrate；
The main component of the filter cake is magnesium hydroxide, and the solute in the filtrate includes organic alkali sulfate；
Preferably, the concentration of magnesium sulfate is 5~30wt% in the liquid phase；
Preferably, the mol ratio of water-soluble organic base and magnesium sulfate sum is 2~3: 1 in the liquid phase；
Preferably, any one of the water-soluble organic base in diethylamine, di-n-propylamine, butylamine, pyrrolidines, piperidines
Or it is a variety of；
Preferably, the reaction temperature is 5~100 DEG C, and the reaction time is 30~300min.
(4) will calcium hydroxide add step (3) obtain filtrate in be reacted, reaction terminate after filter, obtain filter cake with
Filtrate, using at least a portion in filtrate as step (1) raw material；
The filter cake main component is calcium sulfate, and water-soluble organic base is contained in the filtrate；
Preferably, reaction temperature is 5~60 DEG C, 30~60min of reaction time in the step (4)；Calcium hydroxide and filter
Water-soluble organic base sulfate mol ratio is 1.1~1.3: 1 in liquid.
Preferably, the filtrate return to step (3) obtained in the step (4) is recycled.
(5) ammonium bicarbonate solution obtained step (2) and the filter cake obtained to step (4) are reacted, filtering, and obtaining filtrate is
Ammonium sulfate, using filtrate as step (1) raw material.
Preferably, the mol ratio of calcium sulfate is 1.05~1.1: 1 in carbon ammonium and filter cake；
Preferably, reaction temperature is 5~100 DEG C.
The general principle of technique can be described by following chemical equations：
CaCO3+MgCO3+2(NH4)2SO4=CaSO4↓+MgSO4+2(NH4)2CO3 ①
MgSO4+RNH+H2O→Mg(OH)2↓+(RNH2)2SO4 ②
(RNH2)2SO4+Ca(OH)2→CaSO4↓+RNH+H2O ③
CaSO4+(NH4)2CO3=CaCO3↓+(NH4)2SO4 ④
1. dolomite or magnesite carry out obtaining carbon ammonium while separating calcium and magnesium is realized in decomposition by ammonium sulfate；
2. magnesium sulfate synthesizes magnesium hydroxide while obtaining sulfuric acid organic amine salt with water-soluble organic amine；
3. reclaim organic amine with quick lime and the reaction of sulfuric acid organic amine salt and obtain calcium sulfate simultaneously；
4. calcium sulfate reclaims ammonium sulfate simultaneously with carbon ammonium synthetic calcium carbonate.
Said process realizes recycling for ammonium sulfate and organic amine, and raw material is transformed into beneficial product, while base
Originally the zero-emission of useless solid waste liquid waste gas is realized.
In summary, the method that calcium-magnesium-containing carbonate mine of the invention prepares magnesium hydroxide, has the advantages that：
(1) present invention uses ammonium sulfate Wet Decomposition calcium carbonate and magnesium carbonate miberal powder, greatly reduces traditional handicraft dinectly bruning
Required high energy consumption, while obtained high pressure mixing steam is made heat integration, reduced into by fractional condensaion mode
This.
(2) present invention utilizes Ca (OH)2Following for water-soluble organic base and ammonium sulfate is realized with the obtained ammonium bicarbonate solution of reaction
Ring is utilized, and remaining component is converted to high value-added product, not only avoid technical process wastage of material and the dirt to environment
Dye, while improving productivity effect.
(3) as the precipitating reagent of magnesium hydroxide the pH of reaction solution can be made to maintain high value with water-soluble organic base, from
And making magnesium ion precipitation completely, the yield of magnesium hydroxide reaches more than 99%, while sulfate radical reclaims thorough；Compared to more traditional
Ammonia-soda process synthesizes magnesium hydroxide technique, substantially increases the utilization rate of magnesium ion, and the magnesium hydroxide synthesized with the inventive method
It is easy to washing, moisture content is low, and product quality is also improved.
(4) in traditional handicraft general by-product obtain be low secondary valence value gypsum, it is not disposable, easily cause environment dirty
Dye, and by-product precipitated calcium carbonate of the present invention, effectively increase the economic value of byproduct.
Brief description of the drawings
Fig. 1 calcium-magnesium-containing carbonate mines prepare the Simple process figure of magnesium hydroxide.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.It should be clear that the process equipment or device that are not indicated specifically in the following example
Use conventional equipment or device in the art.In addition, it is to be understood that the one or more method and steps mentioned in the present invention are simultaneously
Other method step can also be present or may be used also between the step of these are specifically mentioned by not repelling before and after the combination step
To insert other method step, unless otherwise indicated；It should also be understood that the one or more equipment/devices mentioned in the present invention it
Between combination annexation do not repel and can also have other equipment/device before and after the unit equipment/device or at this
Other equipment/device can also be inserted between the two equipment/devices specifically mentioned a bit, unless otherwise indicated.Moreover, unless another
It is described, the numbering of various method steps is only the convenient tool for differentiating various method steps, rather than is the row of limitation various method steps
Row order limits enforceable scope of the invention, being altered or modified for its relativeness, and technology contents are being changed without essence
In the case of, when being also considered as enforceable category of the invention.
It is the Simple process figure of the present invention referring to Fig. 1.
Embodiment 1
(1) concentration is fitted into autoclave for 15wt% ammonium sulfate and dolomite miberal powder, control ammonium root from
The mol ratio NH of son and calcium ions and magnesium ions in dolomite miberal powder4 +：(Ca2++Mg2+)=2：1, controlling reaction temperature is 220 DEG C, reaction
Pressure is 2.5Mpa, after reaction completely, and it is 220 DEG C that gas phase, which obtains temperature, and pressure is 2.5MPa ammonia, carbon dioxide and water
High pressure mixing steam, the solute of liquid phase includes Adlerika, and solid phase obtains calcium sulfate；
(2) using step 1) the obtained high pressure mixing steam of ammonia, carbon dioxide and water be introduced into one-level evaporator as
Thermal source, the ammonium sulfate for being concentrated by evaporation magnesium sulfate or recovery, evaporating the indirect steam produced is then used for follow-up calcium carbonate
Or magnesium hydroxide products drying, while high temperature mixed vapour partial condensation is used for washing for calcium carbonate product into low concentration ammonium bicarbonate solution
Wash；Uncooled partial high pressure mixed vapour fully enters secondary evaporimeter as the thermal source for being distilled to recover butylamine solution, through distillation
Obtained higher concentration butylamine solution carries out circulation synthesis magnesium hydroxide, vinasse then as magnesium hydroxide products washing lotion and
Process water, while high pressure mixing steam is then all condensed, obtaining the ammonium bicarbonate solution of high concentration is used to synthesize lightweight with calcium sulfate
Calcium carbonate；
(3) by step 1) obtained concentration is at the uniform velocity added in butylamine solution for 5wt% Adlerika, controls sulfuric acid
The mol ratio of magnesium and butylamine is 2: 1, and stirring, reaction temperature is 100 DEG C, and the time is 30min, and filtering, filter cake obtains magnesium hydroxide,
Magnesium ion yield is 98.2%, and filtrate obtains butylamine sulfate, and filter cake is washed, the hydrogen for obtaining that purity is 99.3% is dried
Magnesium oxide product；
(4) by Ca (OH)2It is added to step 3) in obtained butylamine sulfate, control Ca (OH)2With butylamine sulfate mole
Than for 1.1：1, reaction temperature is 60 DEG C, reaction time 30min, after reaction terminates, and filtering, filtrate obtains butylamine solution and returns to step
Rapid 3) to recycle, filter cake obtains calcium sulphate solid；
(5) by step 2) obtained ammonium bicarbonate solution is added to step 4) in obtained calcium sulphate solid, control carbon ammonium and sulphur
The mol ratio of sour calcium is 1.05：1；Reaction temperature is 100 DEG C, after reaction terminates, and filtering, filtrate obtains ammonium sulfate, filter cake
Calcium carbonate solid is obtained, calcium carbonate is scrubbed, drying obtains the CaCO that purity is more than 98wt%3Product, ammonium sulfate circulation
To step 1) continue to decompose dolomite miberal powder.
Following reaction occurs for whole technical process：
CaCO3+MgCO3+2(NH4)2SO4=CaSO4↓+MgSO4+2(NH4)2CO3 1)
MgSO4+2C4H11N+2H2O=Mg (OH)2↓+(C4H12N)2SO4 2)
(C4H12N)2SO4+Ca(OH)2=CaSO4↓+2C4H11N+H2O 3)
CaSO4+(NH4)2CO3=CaCO3↓+(NH4)2SO4 4)
Embodiment 2
(1) concentration is fitted into autoclave for 25wt% ammonium sulfate with magnesite powder, controls ammonium ion
With the mol ratio NH of magnesium ion in magnesite miberal powder4+∶Mg2+=2.5: 1, controlling reaction temperature is 180 DEG C, and reaction pressure is
1.5Mpa, after reaction completely, it is 180 DEG C that gas phase, which obtains temperature, and pressure mixes for the high pressure of 1.5MPa ammonia, carbon dioxide and water
Steam is closed, liquid phase obtains Adlerika, and solid phase obtains calcium sulfate；
(2) using step 1) the obtained high pressure mixing steam of ammonia, carbon dioxide and water be introduced into one-level evaporator as
Thermal source, the ammonium sulfate for being concentrated by evaporation magnesium sulfate or recovery, evaporating the indirect steam produced is then used for follow-up calcium carbonate
Or magnesium hydroxide products drying, while high temperature mixed vapour partial condensation is used for washing for calcium carbonate product into low concentration ammonium bicarbonate solution
Wash；Uncooled partial high pressure mixed vapour fully enters secondary evaporimeter as the thermal source for being distilled to recover piperidine solution, through distillation
Obtained higher concentration piperidine solution carries out circulation synthesis magnesium hydroxide, vinasse then as magnesium hydroxide products washing lotion and
Process water, while high pressure mixing steam is then all condensed, obtaining the ammonium bicarbonate solution of high concentration is used to synthesize lightweight with calcium sulfate
Calcium carbonate；
(3) by step 1) obtained concentration is at the uniform velocity added in piperidine solution for 20wt% Adlerika, controls sulphur
The mol ratio of sour magnesium and piperidines is 2.5：1, stirring, reaction temperature is 50 DEG C, and the time is 150min, and filtering, filter cake obtains hydrogen-oxygen
Change magnesium, magnesium ion yield is 99.2%, and filtrate obtains piperidines sulfate, filter cake is washed, is dried and is obtained purity and be
99.4% magnesium hydroxide products；
(4) by Ca (OH)2It is added to step 3) in obtained piperidines sulfate, control Ca (OH)2With piperidines sulfate mole
Than for 1.2：1, reaction temperature is 40 DEG C, reaction time 40min, after reaction terminates, and filtering, filtrate obtains piperidine solution and returns to step
Rapid 3) to recycle, filter cake obtains calcium sulphate solid；
(5) by step 2) obtained ammonium bicarbonate solution is added to step 4) in obtained calcium sulphate solid, control carbon ammonium and sulphur
The mol ratio of sour calcium is 1.08：1；Reaction temperature is 60 DEG C, after reaction terminates, and filtering, filtrate obtains ammonium sulfate, and filter cake is obtained
To calcium carbonate solid, calcium carbonate is scrubbed, drying obtains the CaCO that purity is more than 98wt%3Product, ammonium sulfate is recycled to
Step 1) continue to decompose magnesite powder.
Following reaction occurs for whole technical process：
MgCO3+(NH4)2SO4=MgSO4+(NH4)2CO3 1)
MgSO4+2C5H11N+2H2O=Mg (OH)2↓+(C5H12N)2SO4 2)
(C5H12N)2SO4+Ca(OH)2=CaSO4↓+2C5H11N+2H2O 3)
CaSO4+(NH4)2CO3=CaCO3↓+(NH4)2SO4 4)
Embodiment 3
(1) concentration is fitted into autoclave for 40wt% ammonium sulfate and dolomite miberal powder, control ammonium root from
The mol ratio NH of son and calcium ions and magnesium ions in dolomite miberal powder4+∶Mg2+=3: 1, controlling reaction temperature is 140 DEG C, and reaction pressure is
0.4Mpa, after reaction completely, it is 140 DEG C that gas phase, which obtains temperature, and pressure mixes for the high pressure of 0.4MPa ammonia, carbon dioxide and water
Steam is closed, liquid phase obtains Adlerika, and solid phase obtains calcium sulfate；
(2) using step 1) the obtained high pressure mixing steam of ammonia, carbon dioxide and water be introduced into one-level evaporator as
Thermal source, the ammonium sulfate for being concentrated by evaporation magnesium sulfate or recovery, evaporating the indirect steam produced is then used for follow-up calcium carbonate
Or magnesium hydroxide products drying, while high temperature mixed vapour partial condensation is used for washing for calcium carbonate product into low concentration ammonium bicarbonate solution
Wash；Uncooled partial high pressure mixed vapour fully enters secondary evaporimeter as the thermal source for being distilled to recover pyrrolidines solution, through steaming
Evaporate obtained higher concentration pyrrolidines solution and carry out circulation synthesis magnesium hydroxide, vinasse then washing as magnesium hydroxide products
Liquid and process water, while high pressure mixing steam is then all condensed, obtaining the ammonium bicarbonate solution of high concentration is used to synthesize with calcium sulfate
Precipitated calcium carbonate；
(3) by step 1) obtained concentration is at the uniform velocity added in pyrrolidines solution for 30wt% Adlerika, controls
The mol ratio of magnesium sulfate and pyrrolidines is 3: 1, and stirring, reaction temperature is 5 DEG C, and the reaction time is 300min, and filtering, filter cake is obtained
Magnesium hydroxide, magnesium ion yield is 99.6%, and filtrate obtains pyrroles's alkyl sulfate, and filter cake is washed, dries and obtains purity
For 99.5% magnesium hydroxide products；
(4) by Ca (OH)2It is added to step 3) in obtained pyrroles's alkyl sulfate, control Ca (OH)2With pyrroles's alkyl sulfate
Mol ratio is 1.3: 1, and reaction temperature is 5 DEG C, reaction time 60min, after reaction terminates, and filtering, filtrate obtains pyrrolidines solution
Return to step 3) recycle, filter cake obtains calcium sulphate solid；
(5) by step 2) obtained ammonium bicarbonate solution is added to step 4) in obtained calcium sulphate solid, control carbon ammonium and sulphur
The mol ratio of sour calcium is 1.1: 1；Reaction temperature is 5 DEG C, after reaction terminates, and filtering, filtrate obtains ammonium sulfate, and filter cake is obtained
Calcium carbonate solid, calcium carbonate is scrubbed, drying obtains the CaCO that purity is more than 98wt%3Product, ammonium sulfate is recycled to step
It is rapid 1) to continue to decompose dolomite miberal powder.
Following reaction occurs for whole technical process：
CaCO3+MgCO3+2(NH4)2SO4=CaSO4↓+MgSO4+2(NH4)2CO3 1)
MgSO4+2C4H9N+2H2O=Mg (OH)2↓+(C4H10N)2SO4 2)
(C4H10N)2SO4+Ca(OH)2=CaSO4↓+2C4H9N+H2O 3)
CaSO4+(NH4)2CO3=CaCO3↓+(NH4)2SO4 4)
Embodiment above is, in order to illustrate embodiment disclosed by the invention, can not to be interpreted as the limit to the present invention
System.In addition, method, the change of composition in various modifications listed herein and invention, are not departing from the scope of the present invention
Be obvious for those skilled in the art on the premise of spirit.Although having combined a variety of specific of the present invention
Preferred embodiment has carried out specific description to the present invention, it is to be understood that, the present invention should not be limited only to these specific embodiments.
In fact, various modifications obvious for those skilled in the art as described above should all include to obtain invention
Within the scope of the invention.
Claims (8)
1. a kind of method that calcium-magnesium-containing carbonate mine prepares magnesium hydroxide, at least comprises the following steps：
(1) ammonium sulfate solution and calcium-magnesium-containing carbonate mine are added into autoclave to be reacted, reaction product separation is obtained
Gas phase, liquid phase and solid phase；
(2) the gas phase fractional condensaion for obtaining step (1) obtains ammonium bicarbonate solution；
(3) liquid phase for obtaining step (1) is added in water-soluble organic alkali solution, is stirred, and is filtered, is filtered after reaction completely
Cake and filtrate；
(4) calcium hydroxide is added and reacted in the filtrate that step (3) is obtained, reaction is filtered after terminating, and obtains filter cake and filtrate,
Using at least a portion in filtrate as step (1) raw material；
(5) ammonium bicarbonate solution obtained step (2) and the filter cake obtained to step (4), are reacted, filtering, are obtained filtrate, will be filtered
At least a portion in liquid as step (1) raw material.
2. the method that calcium-magnesium-containing carbonate mine according to claim 1 prepares magnesium hydroxide, it is characterised in that：The step
(1) calcium-magnesium-containing carbonate mine is magnesite or dolomite mineral in, and 15~40wt% of the ammonium sulfate concentration, the ammonium salt is molten
The mol ratio of calcium ions and magnesium ions is NH in ammonium ion and calcium-magnesium-containing carbonate mine in liquid4 +：(Ca2++Mg2+)=(3~2)：1.
3. the method that calcium-magnesium-containing carbonate mine according to claim 1 prepares magnesium hydroxide, it is characterised in that：The step
(1) any one or a few in following technical characteristic is also included；
A. the reaction temperature is 140~220 DEG C, and reaction pressure is 0.4~2.5Mpa；
B. the mixed vapour temperature is 140~220 DEG C, and pressure is 0.4~2.5Mpa.
4. the method that calcium-magnesium-containing carbonate mine according to claim 1 prepares magnesium hydroxide, it is characterised in that：The step
(2) fractional condensaion in includes one-level and condensed and B-grade condensation, and the one-level condensation refers to the gas phase one obtained in step (1)
The liquid phase of the filtrate or acquisition in step (1) entered for heating medium in one-level evaporator concentration and recovery step (5) is allocated as, together
When by the indirect steam produced in evaporation process be used for baking step (1) in obtain solid phase or step (3) in obtain filter
Cake；Another part gas phase in step (1) enters secondary condenser, for the thermal source of the filtrate obtained in distilation steps (5).
5. the method that calcium-magnesium-containing carbonate mine according to claim 4 prepares magnesium hydroxide, it is characterised in that：Described two grades
Vinasse solution is obtained in condensation is used for process water and cleaning magnesium hydroxide；Into the vapor condensation of secondary condenser into carbon
Ammonium salt solution and be used for and calcium sulfate reaction generation calcium carbonate.
6. the method that calcium-magnesium-containing carbonate mine according to claim 1 prepares magnesium hydroxide, it is characterised in that：The step
(3) any one or a few in following technical characteristic is also included：
A. the concentration of magnesium sulfate is 5~30wt% in the liquid phase；
B. the mol ratio of magnesium sulfate and water-soluble organic base is 2~3 in the liquid phase：1；
C. any one or more of the water-soluble organic base in diethylamine, di-n-propylamine, butylamine, pyrrolidines, piperidines,
D. the reaction temperature is 5~100 DEG C, and the reaction time is 30~300min.
7. the method that calcium-magnesium-containing carbonate mine according to claim 1 prepares magnesium hydroxide, it is characterised in that：The step
(4) reaction temperature is 5~60 DEG C, 30~60min of reaction time in；Calcium hydroxide rubs with water-soluble organic base sulfate in filtrate
You are than being 1.1~1.3：1.
8. the method that calcium-magnesium-containing carbonate mine according to claim 1 prepares magnesium hydroxide, it is characterised in that：The step
(5) any one or a few in following characteristics is also included：
A. the mol ratio of calcium sulfate is 1.05~1.1 in carbon ammonium and filter cake in ammonium bicarbonate solution：1；
B. reaction temperature is 5~100 DEG C.
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