CN106865579B - Well mine sea lake salt brine thermal cycling method ammonia integrated soda production - Google Patents
Well mine sea lake salt brine thermal cycling method ammonia integrated soda production Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/18—Preparation by the ammonia-soda process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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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
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
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Abstract
A kind of well mine sea lake salt brine thermal cycling method ammonia integrated soda production, using well mine sea lake salt brine as raw material, with ammonium mother liquor processed and a part of deamination mother liquor magnesium hydroxide, calcium sulfate and sulphur removal brine are refining to obtain with lime reaction, sulphur removal brine is added soda ash and obtains refined brine and calcium carbonate, refined brine and acquisition sodium bicarbonate after ammonia, carbon dioxide reaction and weight alkali liquor；Ammonia, carbon dioxide and deamination mother liquor are obtained after weight alkali liquor removing ammonium hydrogen carbonate, ammonium carbonate；A part of isolated solid ammonium chloride of deamination mother liquid evaporation and ammonium mother liquor processed, another part are incorporated in raw material, and wherein ammonium chloride obtains ammonia, calcium chloride with a part of lime reaction, and calcium chloride is reacted with sodium sulphate generates calcium sulfate；Magnesium sulfate, magnesium chloride and another part lime reaction generate calcium sulfate and magnesium hydrate precipitate object in raw material；Sulphur removal brine after separating calcium sulphate and magnesium hydrate precipitate object is added soda ash and obtains refined brine and lime deposit；The refined brine continues above-mentioned metathesis reaction.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, especially a kind of directly using well mine sea lake salt brine as raw material, use
Thermal cycling method produces soda ash, ammonium chloride, calcium chloride process.
Background technology
Known production soda ash technique has leblanc process, ammonia-soda process and cold process union soda, wherein：1) Leblanc legal system is pure
Alkali：Leblanc process there are poor product quality, production cost is high, manpower consumption is big and production process carries out between solid phase, difficult
In work continuously the shortcomings of；2) Sol ties up method alkaline：Sol ties up the low (utilization rate of sodium of method (ammonia-soda process) raw material chlorination sodium utilization
About 75%, chlorine utilization 0%), slops (containing a large amount of calcium chloride, sodium chloride, often produces 1 ton of soda ash and generates 9-
10m3Discharging of waste liquid) discharge system amount is very big, and it wastes resource, form new environmental pollution；3) combine legal system soda ash (cold process
Union soda)：Solid sodium chloride need to be used for raw material, cost of material is higher, and cold analysis salting-out crystallization ammonium chloride power consumption is higher, no
It can directly use well mine sea lake salt brine for raw material.Therefore, application has limitation to above-mentioned technique in actual production.
Invention content
The object of the present invention is to provide a kind of well mine sea lake salt brine thermal cycling method ammonia integrated soda production, dropped in production process
Low energy consumption and cost, no mother liquor discharge, sodium and chlorion theoretical recovery 100% are a kind of solution environmental protections, energy saving subtract
The green cleansing preparation method of making of row.
To achieve the above object, the present invention takes following technical scheme：
A kind of well mine sea lake salt brine thermal cycling method ammonia integrated soda production, it includes the following steps：
1) using well mine sea lake salt brine as raw material, after being mixed with ammonium mother liquor processed and a part of deamination mother liquor with lime reaction with
Lime, calcium chloride are refined to remove magnesium, sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation object and sulphur removal brine, sulphur removal brine
It is added after soda ash removes calcium ion and obtains refined brine and lime deposit, which is raw material with ammonia, carbon dioxide
Separation obtains solid sodium bicarbonate and contains ammonium chloride, sodium chloride, ammonium hydrogen carbonate, ammonium carbonate and sulfuric acid after carrying out metathesis reaction
The heavy alkali liquor of sodium；
2) ammonia, carbon dioxide will be obtained after heavy alkali liquor preheating high temperature removal ammonium hydrogen carbonate, the ammonium carbonate and contains chlorination
The deamination mother liquor of ammonium, sodium chloride and sodium sulphate；
3) a part of deamination mother liquor is through the isolated solid ammonium chloride of pervaporation and ammonium mother liquor processed；
4) another part deamination mother liquor is incorporated in the raw material in step 1), and ammonium chloride therein is obtained with a part of lime reaction
To ammonia, calcium chloride, the reaction was continued the generation of calcium chloride and the sodium sulphate in well mine sea lake salt raw brine and ammonium mother liquor mixed liquor processed
Calcium sulfate precipitation object；Magnesium sulfate in well mine sea lake salt raw brine, magnesium chloride and another part lime reaction generate calcium sulfate and
Magnesium hydrate precipitate object；
5) it is anti-that calcium sulfate in soda ash, with sulphur removal brine is added in the sulphur removal brine after separating calcium sulphate and magnesium hydrate precipitate object
It should obtain refined brine and lime deposit；
6) refined brine carries out the process that metathesis reaction in step 1) carries out subsequent cycle production soda ash.
Further, each component content is NaCl 1-360g/l, Na in the well mine sea lake salt raw brine2SO4 1-
360g/l、MgSO4 0.1-30g/l、CaSO4 0.1-6.0g/l、MgCl2 0.1-30g/l、CaCl2 0.1-6g/l。
Further, the ammonia obtained during the deamination in the step 2) and in the step 4) participates in the step 1)
Middle refined brine inhales ammonia；The carbon dioxide recovery obtained during deamination in the step 2) is for ammonia salt in the step 1)
Water is carbonized.
Further, it obtains solid sodium bicarbonate in the step 1) and is converted into solid sodium carbonate after calcining.
Further, the solid ammonium chloride in the step 3) distills to obtain the ammonia that ammonia is inhaled for refined brine using lime
And by-product calcium chloride product.
Further, the lime deposit recycling in the step 5) produces lime as raw material.
Further, each component content is NH in the ammonium mother liquor processed4Cl 5-450g/l、Na2SO4 1-55g/l、NaCl
5-360g/l。
Further, the metathesis reaction temperature in the step 1) is 15-50 DEG C；Reaction temperature in the step 2)
It is 55-150 DEG C.
Further, each component content is NaCl 1-360g/l, Na in the refined brine2SO40.104-55g/l；Institute
It is NH to state each component content in deamination mother liquor4Cl 5-450g/l、Na2SO4 1-55g/l、NaCl 5-360g/l。
Further, each component content is NaCl 1-360g/l, CaSO in the sulphur removal brine4 0.1-6.0g/l。
This process well mine sea lake salt brine can also be NaCl-H2O (such as caustic soda light salt brine fine), Na2SO4-H2O (such as ten water awns
Nitre) system and ammonia (NH3), carbon dioxide (CO2) it is that raw material produces soda ash, ammonium chloride, calcium chloride product.
The beneficial effects of the invention are as follows：Well mine sea lake salt brine thermal cycling method ammonia integrated soda production of the present invention, production process
In reduce energy consumption and cost, no mother liquor discharge, sodium and chlorion theoretical recovery 100% are a kind of solutions environmental protections, save
The green cleansing preparation method of making of energy emission reduction.
Description of the drawings
Fig. 1 is the process flow chart of well mine sea lake salt brine thermal cycling method ammonia integrated soda production of the present invention.
Specific implementation mode
As shown in Figure 1, the present invention provides a kind of well mine sea lake salt brine thermal cycling method ammonia integrated soda production, with well mine sea lake salt
Brine is raw material, after being mixed with ammonium mother liquor processed and a part of deamination mother liquor with lime reaction with lime, calcium chloride it is refined remove magnesium,
Sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation object and sulphur removal brine, and sulphur removal brine is added after soda ash removes calcium ion and obtains
To refined brine and lime deposit, which detaches after being raw material progress metathesis reaction with ammonia, carbon dioxide and obtains
Obtain solid sodium bicarbonate and the heavy alkali liquor containing ammonium chloride, sodium chloride, ammonium hydrogen carbonate, ammonium carbonate and sodium sulphate；By the heavy alkali
Ammonia, carbon dioxide are obtained after mother liquor preheating high temperature removal ammonium hydrogen carbonate, ammonium carbonate and containing ammonium chloride, sodium chloride and sodium sulphate
Deamination mother liquor；A part of deamination mother liquor is through the isolated solid ammonium chloride of pervaporation and ammonium mother liquor processed；Another part deamination mother liquor
It is incorporated in well mine sea lake salt raw brine, ammonium chloride therein obtains ammonia, calcium chloride, calcium chloride and well with a part of lime reaction
The reaction was continued generates calcium sulfate precipitation object for sodium sulphate in mine sea lake salt raw brine and ammonium mother liquor mixed liquor processed；Well mine sea lake salt
Magnesium sulfate, magnesium chloride and another part lime reaction generate calcium sulfate and magnesium hydrate precipitate object in raw brine；Detach sulfuric acid
Sulphur removal brine after calcium and magnesium hydrate precipitate object is added calcium sulfate in soda ash, with sulphur removal brine and refined brine and carbon is obtained by the reaction
Sour Ca-deposit；The refined brine carries out the process that above-mentioned metathesis reaction carries out subsequent cycle production soda ash.
Being exemplified below several specific embodiments, the present invention is described in detail.
Embodiment 1：Take 100m3Raw material (rock salt brine) (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、
CaSO42.0g/l) and 170m3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.94g/l, NaCl 220g/l) and 6.34m3
Deamination mother liquor, with lime, the refined removing magnesium of calcium chloride, sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation with lime reaction
Object and sulphur removal brine, sulphur removal brine are added after soda ash removes calcium ion and obtain refined brine and lime deposit, refine rock salt
The 276.34m obtained after brine3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2)
Carrying out metathesis reaction (30 DEG C of reaction temperature) for raw material, separation obtains 43 tons of solid sodium bicarbonate (NaHCO afterwards3) and 276.34m3
Contain ammonium chloride, sodium chloride and sodium sulphate (NaCl 138g/l, Na2SO4 6.26g/l、NH4Cl 220g/l) and ammonium hydrogen carbonate
(NH4HCO3), ammonium carbonate ((NH4)2CO3) heavy alkali liquor；Weight alkali liquor is preheated into high temperature (110 DEG C of temperature) and removes ammonium hydrogen carbonate
(NH4HCO3), ammonium carbonate ((NH4)2CO3) after obtain ammonia (NH3), carbon dioxide (CO2) and 276.34m3Contain ammonium chloride, chlorination
Sodium and sodium sulphate (NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) deamination mother liquor；6.34m3Deamination mother liquor
(NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) be incorporated in raw material pass through and 1.68 tons of lime (Ca (OH)2) anti-
(50 DEG C of reaction temperature) is answered to obtain ammonia (NH3), 2.50 tons of calcium chloride (CaCl2), 2.50 tons of calcium chloride (CaCl2) and 276.34m3
Mix 3.23 tons of sodium sulphate (Na in brine2SO4) the reaction was continued generate 3.09 tons of calcium sulfate (CaSO4) sediment；100m3Rock salt
Brine (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、CaSO40.03 ton of magnesium sulfate (MgSO in 2.0g/l)4)
0.0210 ton of calcium sulfate (CaSO is generated with 0.0185 ton of lime reaction (50 DEG C of reaction temperature)4) and 0.0145 ton of magnesium hydroxide
(Mg(OH)2) sediment；276.34m3Weight alkali liquor deamination process and 6.34m3Part ammonium chloride passes through and 1.68 in deamination mother liquor
Ammonia (the NH that ton lime reaction obtains3) recycle the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) recycle for ammonia
Brine is carbonized；Separating calcium sulphate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m after sediment3Sulphur removal halogen
Water (NaCl 288g/l, CaSO41.292 tons of soda ash (Na 6.0g/l) are added2CO3) with brine in 1.642 tons of calcium sulfate
(CaSO4) 276.34m is obtained by the reaction3Refined brine (NaCl 288g/l, Na2SO4 6.26g/l) and 1.207 tons of calcium carbonate
(CaCO3) sediment；270m3Deamination mother liquor (NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) through pervaporation point
From obtaining 27 tons of solid product ammonium chloride (NH4) and 170m Cl3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO4 9.44g/l、
NaCl 220g/l)；100m3Rock salt brine (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、CaSO4 2.0g/l)
With 170m3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.44g/l, NaCl 220g/l) and 6.34m3Deamination mother liquor mixes
Liquid refined refined brine (NaCl 288g/l, Na after removing magnesium, sulfate radical, calcium ion2SO46.26g/l) inhale the life of ammonia subsequent cycle
Produce soda ash process；43 tons of solid sodium bicarbonate (NaHCO3) 27 tons of solid sodium carbonate (Na are converted into after calcining2CO3)；27 tons of solids
Ammonium chloride (NH4Cl lime (Ca (OH)) is used2) distillation, then it can recycle ammonia (NH3) for refined brine suction ammonia, carbon dioxide
(CO2) recycle for 28 tons of ammonial brine carbonization, by-product calcium chloride (CaCl2) product；1.207 tons of calcium carbonate mud of refined brine by-product
(CaCO3) it is recycled as the raw material of production lime.
Embodiment 2：Take 100m3Raw material (sea salt brine) (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、
CaSO42.0g/l) and 170m3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.94g/l, NaCl 220g/l) and 6.34m3
Deamination mother liquor, with lime, the refined removing magnesium of calcium chloride, sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation with lime reaction
Object and sulphur removal brine, sulphur removal brine are added after soda ash removes calcium ion and obtain refined brine and lime deposit, after refining
The 276.34m arrived3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) be raw material into
Row metathesis reaction (30 DEG C of reaction temperature) detaches afterwards obtains 43 tons of solid sodium bicarbonate (NaHCO3) and 276.34m3Contain chlorination
Ammonium, sodium chloride and sodium sulphate (NaCl 138g/l, Na2SO4 6.26g/l、NH4Cl 220g/l) and ammonium hydrogen carbonate (NH4HCO3)、
Ammonium carbonate ((NH4)2CO3) heavy alkali liquor；Weight alkali liquor is preheated into high temperature (110 DEG C of temperature) and removes ammonium hydrogen carbonate (NH4HCO3)、
Ammonium carbonate ((NH4)2CO3) after obtain ammonia (NH3), carbon dioxide (CO2) and 276.34m3Contain ammonium chloride, sodium chloride and sodium sulphate
(NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) deamination mother liquor；6.34m3Deamination mother liquor (NH4Cl 220g/
l、Na2SO46.26g/l, NaCl 138g/l) it is incorporated in raw material and passes through and 1.68 tons of lime (Ca (OH)2) reaction (reaction temperature
50 DEG C) obtain ammonia (NH3), 2.50 tons of calcium chloride (CaCl2), 2.50 tons of calcium chloride (CaCl2) and 276.34m3It mixes in brine
3.23 tons of sodium sulphate (Na2SO4) the reaction was continued generate 3.09 tons of calcium sulfate (CaSO4) sediment；100m3Sea salt brine (NaCl
300g/l、Na2SO4 15g/l、MgSO4 0.30g/l、CaSO40.03 ton of magnesium sulfate (MgSO in 2.0g/l)4) and 0.0185 ton
Lime reaction (50 DEG C of reaction temperature) generates 0.0210 ton of calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) precipitation
Object；276.34m3Weight alkali liquor deamination process and 6.34m3Part ammonium chloride with 1.68 tons of lime reactions by obtaining in deamination mother liquor
Ammonia (the NH arrived3) recycle the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) recycle for ammonial brine carbonization；Separation
Calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m after sediment3Sulphur removal brine (NaCl 288g/
l、CaSO41.292 tons of soda ash (Na 6.0g/l) are added2CO3) with brine in 1.642 tons of calcium sulfate (CaSO4) be obtained by the reaction
276.34m3Refined brine (NaCl288g/l, Na2SO46.26g/l) and 1.207 tons of calcium carbonate (CaCO3) sediment；270m3It is de-
Ammonia mother liquor (NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) through the isolated 27 tons of solid product chlorine of pervaporation
Change ammonium (NH4) and 170m Cl3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.44g/l、NaCl 220g/l)；100m3Sea salt
Brine (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、CaSO42.0g/l) and 170m3Ammonium mother liquor (NH processed4Cl
190.6g/l、Na2SO49.44g/l, NaCl 220g/l) and 6.34m3Deamination mother liquor mixed liquor is refined to remove magnesium, sulfate radical, calcium
Refined brine (NaCl 288g/l, Na after ion2SO4It 6.26g/l) inhales ammonia subsequent cycle and produces soda ash process；43 tons of solid carbons
Sour hydrogen sodium (NaHCO3) 27 tons of solid sodium carbonate (Na are converted into after calcining2CO3)；27 tons of solid ammonium chloride (NH4Cl lime) is used
(Ca(OH)2) distillation, then it can recycle ammonia (NH3) for refined brine suction ammonia, carbon dioxide (CO2) recycle for ammonial brine carbon
Change, 28 tons of calcium chloride (CaCl of by-product2) product；1.207 tons of calcium carbonate mud (CaCO of refined brine by-product3) it is recycled as production stone
The raw material of ash.
Embodiment 3：Take 100m3Lake salt brine (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、CaSO4
2.0g/l) and 170m3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.94g/l, NaCl 220g/l) and 6.34m3Deamination is female
Liquid, with lime, the refined removing magnesium of calcium chloride, sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation object and removes with lime reaction
Sulphur brine, sulphur removal brine are added after soda ash removes calcium ion and obtain refined brine and lime deposit, obtained after refined
276.34m3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) it is that raw material is answered
Decomposition reaction (30 DEG C of reaction temperature) detaches afterwards obtains 43 tons of solid sodium bicarbonate (NaHCO3) and 276.34m3Containing ammonium chloride,
Sodium chloride and sodium sulphate (NaCl 138g/l, Na2SO4 6.26g/l、NH4Cl 220g/l) and ammonium hydrogen carbonate (NH4HCO3), carbonic acid
Ammonium ((NH4)2CO3) heavy alkali liquor；Weight alkali liquor is preheated into high temperature (110 DEG C of temperature) and removes ammonium hydrogen carbonate (NH4HCO3), carbonic acid
Ammonium ((NH4)2CO3) after obtain ammonia (NH3), carbon dioxide (CO2) and 276.34m3Contain ammonium chloride, sodium chloride and sodium sulphate
(NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) deamination mother liquor；6.34m3Deamination mother liquor (NH4Cl 220g/
l、Na2SO46.26g/l, NaCl 138g/l) it is incorporated in raw material and passes through and 1.68 tons of lime (Ca (OH)2) reaction (reaction temperature
50 DEG C) obtain ammonia (NH3), 2.50 tons of calcium chloride (CaCl2), 2.50 tons of calcium chloride (CaCl2) and 276.34m3It mixes in brine
3.23 ton sodium sulphate (Na2SO4) the reaction was continued generate 3.09 tons of calcium sulfate (CaSO4) sediment；100m3Lake salt brine (NaCl
300g/l、Na2SO4 15g/l、MgSO4 0.30g/l、CaSO40.03 ton of magnesium sulfate (MgSO in 2.0g/l)4) and 0.0185 ton
Lime reaction (50 DEG C of reaction temperature) generates 0.0210 ton of calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) precipitation
Object；276.34m3Weight alkali liquor deamination process and 6.34m3Part ammonium chloride with 1.68 tons of lime reactions by obtaining in deamination mother liquor
Ammonia (the NH arrived3) recycle the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) recycle for ammonial brine carbonization；Separation
Calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m after sediment3Sulphur removal brine (NaCl 288g/
l、CaSO41.292 tons of soda ash (Na 6.0g/l) are added2CO3) with brine in 1.642 tons of calcium sulfate (CaSO4) be obtained by the reaction
276.34m3Refined brine (NaCl 288g/l, Na2SO46.26g/l) and 1.207 tons of calcium carbonate (CaCO3) sediment；270m3
Deamination mother liquor (NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) through the isolated 27 tons of solid products of pervaporation
Ammonium chloride (NH4) and 170m Cl3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.44g/l、NaCl 220g/l)；100m3Lake
Bittern water (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、CaSO42.0g/l) and 170m3Ammonium mother liquor processed
(NH4Cl 190.6g/l、Na2SO49.44g/l, NaCl 220g/l) and 6.34m3Deamination mother liquor mixed liquor is refined to remove magnesium, sulphur
Refined brine (NaCl 288g/l, Na after acid group, calcium ion2SO4It 6.26g/l) inhales ammonia subsequent cycle and produces soda ash process；43 tons
Solid sodium bicarbonate (NaHCO3) 27 tons of solid sodium carbonate (Na are converted into after calcining2CO3)；27 tons of solid ammonium chloride (NH4Cl it) adopts
With lime (Ca (OH)2) distillation, then it can recycle ammonia (NH3) for refined brine suction ammonia, carbon dioxide (CO2) recycle for ammonia
28 tons of brine carbonization, by-product calcium chloride (CaCl2) product；1.207 tons of calcium carbonate mud (CaCO of refined brine by-product3) be recycled as
Produce the raw material of lime.
Embodiment 4：Take 100m3The light bittern water of caustic soda (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、
CaSO42.0g/l) and 170m3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO49.94g/l, NaCl 220g/l) and 6.34m3
Deamination mother liquor, with lime, the refined removing magnesium of calcium chloride, sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation with lime reaction
Object and sulphur removal brine, sulphur removal brine are added after soda ash removes calcium ion and obtain refined brine and lime deposit, after refining
The 276.34m arrived3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) be raw material into
Row metathesis reaction (30 DEG C of reaction temperature) detaches afterwards obtains 43 tons of solid sodium bicarbonate (NaHCO3) and 276.34m3Contain chlorination
Ammonium, sodium chloride and sodium sulphate (NaCl 138g/l, Na2SO4 6.26g/l、NH4Cl 220g/l) and ammonium hydrogen carbonate (NH4HCO3)、
Ammonium carbonate ((NH4)2CO3) heavy alkali liquor；Weight alkali liquor is preheated into high temperature (110 DEG C of temperature) and removes ammonium hydrogen carbonate (NH4HCO3)、
Ammonium carbonate ((NH4)2CO3) after obtain ammonia (NH3), carbon dioxide (CO2) and 276.34m3Contain ammonium chloride, sodium chloride and sodium sulphate
(NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) deamination mother liquor；6.34m3Deamination mother liquor (NH4Cl 220g/
l、Na2SO46.26g/l, NaCl 138g/l) it is incorporated in raw material and passes through and 1.68 tons of lime (Ca (OH)2) reaction (reaction temperature
50 DEG C) obtain ammonia (NH3), 2.50 tons of calcium chloride (CaCl2), 2.50 tons of calcium chloride (CaCl2) and 276.34m3It mixes in brine
3.23 tons of sodium sulphate (Na2SO4) the reaction was continued generate 3.09 tons of calcium sulfate (CaSO4) sediment；100m3The light bittern water of caustic soda
(NaCl 300g/l、Na2SO4 15g/l、MgSO4 0.30g/l、CaSO40.03 ton of magnesium sulfate (MgSO in 2.0g/l)4) with
0.0185 ton of lime reaction (50 DEG C of reaction temperature) generates 0.0210 ton of calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg
(OH)2) sediment；276.34m3Weight alkali liquor deamination process and 6.34m3Part ammonium chloride passes through and 1.68 tons in deamination mother liquor
Ammonia (the NH that lime reaction obtains3) recycle the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) recycle for ammonia salt
Water is carbonized；Separating calcium sulphate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m3 sulphur removal brine after sediment
(NaCl 288g/l、CaSO41.292 tons of soda ash (Na 6.0g/l) are added2CO3) with brine in 1.642 tons of calcium sulfate (CaSO4)
276.34m is obtained by the reaction3Refined brine (NaCl 288g/l, Na2SO46.26g/l) and 1.207 tons of calcium carbonate (CaCO3) precipitation
Object；270m3Deamination mother liquor (NH4Cl 220g/l、Na2SO46.26g/l, NaCl 138g/l) isolated 27 tons through pervaporation
Solid product ammonium chloride (NH4) and 170m Cl3Ammonium mother liquor (NH processed4Cl 190.6g/l、Na2SO4 9.44g/l、NaCl 220g/
l)；100m3Rock salt brine (NaCl 300g/l, Na2SO4 15g/l、MgSO4 0.30g/l、CaSO42.0g/l) and 170m3System
Ammonium mother liquor (NH4Cl 190.6g/l、Na2SO49.44g/l, NaCl 220g/l) and 6.34m3Deamination mother liquor mixed liquor is refined to be removed
Remove refined brine (NaCl 288g/l, Na after magnesium, sulfate radical, calcium ion2SO4It 6.26g/l) inhales ammonia subsequent cycle and produces soda ash work
Sequence；43 tons of solid sodium bicarbonate (NaHCO3) 27 tons of solid sodium carbonate (Na are converted into after calcining2CO3)；27 tons of solid ammonium chlorides
(NH4Cl lime (Ca (OH)) is used2) distillation, then it can recycle ammonia (NH3) for refined brine suction ammonia, carbon dioxide (CO2) return
It receives for 28 tons of ammonial brine carbonization, by-product calcium chloride (CaCl2) product；1.207 tons of calcium carbonate mud (CaCO of refined brine by-product3)
It is recycled as the raw material of production lime.
Present invention process advantage is：Well mine sea lake salt brine thermal cycling method ammonia integrated soda production produces soda ash, ammonium chloride, chlorination
Calcium product has major-minor product quality high, and adaptability to raw material is strong, sodium and chlorion theoretical yield 100%, comprehensive energy consumption and cost
It is relatively low, the features such as closed cycle three-waste free discharge.
Claims (9)
1. a kind of well mine sea lake salt brine thermal cycling method ammonia integrated soda production, which is characterized in that it includes the following steps：
1) using well mine sea lake salt brine as raw material, with lime reaction with stone after being mixed with ammonium mother liquor processed and a part of deamination mother liquor
Ash, calcium chloride are refined to remove magnesium, sulfate ion, obtains magnesium hydroxide, calcium sulfate precipitation object and sulphur removal brine, sulphur removal brine adds
Enter after soda ash removes calcium ion and obtain refined brine and lime deposit, the refined brine and ammonia, carbon dioxide be raw material into
Separation obtains solid sodium bicarbonate and contains ammonium chloride, sodium chloride, ammonium hydrogen carbonate, ammonium carbonate and sodium sulphate after row metathesis reaction
Heavy alkali liquor；
2) ammonia, carbon dioxide will be obtained after heavy alkali liquor preheating high temperature removal ammonium hydrogen carbonate, the ammonium carbonate and containing ammonium chloride, chlorine
Change the deamination mother liquor of sodium and sodium sulphate；
3) a part of deamination mother liquor is through the isolated solid ammonium chloride of pervaporation and ammonium mother liquor processed；
4) another part deamination mother liquor is incorporated in the raw material in step 1), and ammonium chloride therein is obtained with a part of lime reaction
Ammonia, calcium chloride, sodium sulphate in calcium chloride and well mine sea lake salt raw brine and ammonium mother liquor mixed liquor processed the reaction was continued generation sulphur
Sour Ca-deposit；Magnesium sulfate, magnesium chloride and another part lime reaction generate calcium sulfate and hydrogen in well mine sea lake salt raw brine
Magnesium oxide precipitation object；
5) soda ash is added in the sulphur removal brine after separating calcium sulphate and magnesium hydrate precipitate object, is reacted with calcium sulfate in sulphur removal brine
To refined brine and lime deposit；
6) refined brine carries out the process that metathesis reaction in step 1) carries out subsequent cycle production soda ash.
2. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1, which is characterized in that described
Each component content is NaCl 1-360g/l, Na in well mine sea lake salt raw brine2SO4 1-360g/l、MgSO4 0.1-30g/l、
CaSO4 0.1-6.0g/l、MgCl2 0.1-30g/l、CaCl2 0.1-6g/l。
3. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
The ammonia obtained during deamination in step 2) and in the step 4) participates in refined brine in the step 1) and inhales ammonia；The step
It is rapid 2) in deamination during obtained carbon dioxide recovery in the step 1) with refined brine, that ammonia carries out double decomposition is anti-
It answers.
4. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
Solid sodium bicarbonate is obtained in step 1), and solid sodium carbonate is converted into after calcining.
5. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
Lime deposit recycling in step 5) produces lime as raw material.
6. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
Each component content is NH in ammonium mother liquor processed4Cl 190.6g/l、Na2SO4 9.44g/l、NaCl 220g/l。
7. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
Metathesis reaction temperature in step 1) is 15-50 DEG C；Reaction temperature in the step 2) is 55-150 DEG C.
8. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
Each component content is NaCl 1-360g/l, Na in refined brine2SO40.104-55g/l；Each ingredient contains in the deamination mother liquor
Amount is NH4Cl 220g/l、Na2SO4 6.26g/l、NaCl 138g/l。
9. well mine sea lake salt brine thermal cycling method ammonia integrated soda production according to claim 1 or 2, which is characterized in that described
Each component content is NaCl 1-360g/l, CaSO in sulphur removal brine4 0.1-6.0g/l。
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| CN108529652B (en) * | 2018-04-16 | 2020-05-12 | 黄河三角洲京博化工研究院有限公司 | Resource utilization process of industrial sodium chloride |
| CN110589857A (en) * | 2019-10-29 | 2019-12-20 | 常州大学 | Method for preparing alkali by using waste salt in combination manner |
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| CN112850754B (en) * | 2021-01-26 | 2023-02-07 | 青海盐湖工业股份有限公司 | Soda ash and magnesium alkali co-production system and co-production method |
| CN112723391B (en) * | 2021-02-24 | 2022-11-18 | 彭赛军 | Process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings |
| CN113135582A (en) * | 2021-04-01 | 2021-07-20 | 常州大学 | Production method for jointly preparing sodium carbonate and ammonium chloride by using sodium chloride |
| CN114180601A (en) * | 2021-12-27 | 2022-03-15 | 彭赛军 | Green low-carbon process for producing sodium carbonate and caustic soda from waste salt and waste residues |
| CN114477236B (en) * | 2022-01-28 | 2023-09-15 | 江西晶昊盐化有限公司 | Calcium halide purifying method and pH value adjusting method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU767026A1 (en) * | 1978-03-02 | 1980-09-30 | Предприяие П/Я А-3732 | Method of liquid purification from magnesium and calcium oins |
| CN101708858A (en) * | 2009-11-28 | 2010-05-19 | 大连化工研究设计院 | Method for producing low-salt high-quality dense soda ash |
| CN101837995A (en) * | 2009-03-18 | 2010-09-22 | 中国中轻国际工程有限公司 | NaCl-Na2SO4-H2O system and process for producing NaHCO3, NH4Cl and NaCl from NH4HCO3 |
| CN102153113A (en) * | 2011-03-01 | 2011-08-17 | 中国中轻国际工程有限公司 | Process for producing mirabilite type bittern, sodium carbonate, sodium chloride, sodium sulfate and ammonium chloride |
| CN103880046A (en) * | 2014-03-17 | 2014-06-25 | 中国中轻国际工程有限公司 | Technology for co-production of sodium carbonate, sodium chloride and ammonium chloride through calcium type rock salt brine and flue gas of boiler |
-
2017
- 2017-02-16 CN CN201710084039.XA patent/CN106865579B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU767026A1 (en) * | 1978-03-02 | 1980-09-30 | Предприяие П/Я А-3732 | Method of liquid purification from magnesium and calcium oins |
| CN101837995A (en) * | 2009-03-18 | 2010-09-22 | 中国中轻国际工程有限公司 | NaCl-Na2SO4-H2O system and process for producing NaHCO3, NH4Cl and NaCl from NH4HCO3 |
| CN101708858A (en) * | 2009-11-28 | 2010-05-19 | 大连化工研究设计院 | Method for producing low-salt high-quality dense soda ash |
| CN102153113A (en) * | 2011-03-01 | 2011-08-17 | 中国中轻国际工程有限公司 | Process for producing mirabilite type bittern, sodium carbonate, sodium chloride, sodium sulfate and ammonium chloride |
| CN103880046A (en) * | 2014-03-17 | 2014-06-25 | 中国中轻国际工程有限公司 | Technology for co-production of sodium carbonate, sodium chloride and ammonium chloride through calcium type rock salt brine and flue gas of boiler |
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