CN106865579A - Well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production - Google Patents

Well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production Download PDF

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CN106865579A
CN106865579A CN201710084039.XA CN201710084039A CN106865579A CN 106865579 A CN106865579 A CN 106865579A CN 201710084039 A CN201710084039 A CN 201710084039A CN 106865579 A CN106865579 A CN 106865579A
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bittern
ammonia
ammonium
mother liquor
ore deposit
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CN106865579B (en
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彭赛军
彭志成
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China Zhongqing International Engineering Co Ltd
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China Zhongqing International Engineering Co Ltd
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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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

A kind of well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production, with well ore deposit sea lake salt bittern as raw material, with ammonium mother liquor processed and a part of deamination mother liquor magnesium hydroxide, calcium sulfate and sulphur removal bittern are refining to obtain with lime reaction, sulphur removal bittern adds soda ash to obtain refined brine and calcium carbonate, and sodium acid carbonate and weight alkali liquor are obtained after refined brine and ammonia, carbon dioxide reaction；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 produces calcium sulfate with sodium sulphate reaction；Magnesium sulfate, magnesium chloride and another part lime reaction produce calcium sulfate and magnesium hydrate precipitate thing in raw material；Sulphur removal bittern after separating calcium sulphate and magnesium hydrate precipitate thing adds soda ash to obtain refined brine and lime deposit；The refined brine proceeds above-mentioned metathesis reaction.

Description

Well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production
Technical field
The invention belongs to technical field of inorganic chemical industry, particularly it is a kind of directly with well ore deposit sea lake salt bittern as raw material, use Thermal cycling method production 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 has that poor product quality, production cost are high, manpower consumption is big and production process is carried out between solid phase, difficult The shortcomings of working continuously；2) Sol dimension 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 is for 0%), slops (containing a large amount of calcium chloride, sodium chloride, often produces 1 ton of soda ash and produces 9- 10m3Discharging of waste liquid) discharge system amount greatly, waste resource, form new environmental pollution；3) legal system soda ash (cold process is combined Union soda)：It is raw material that solid sodium chloride need to be used, and cost of material is higher, and cold analysis salting-out crystallization ammonium chloride power consumption is higher, no It is raw material that well ore deposit sea lake salt bittern can directly be used.Therefore, above-mentioned technique is applied in actual production limitation.
The content of the invention
It is an object of the invention to provide a kind of well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production, dropped in its production process Low energy consumption and cost, without mother liquor discharge, sodium and chlorion theoretical recovery 100% are a kind of to solve environmental protection, energy-conservation and 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 ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production, it is comprised the following steps：
1) with well ore deposit sea lake salt bittern as raw material, after mixing 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 thing and sulphur removal bittern, sulphur removal bittern Soda ash is added to obtain refined brine and lime deposit after removing calcium ion, the refined brine 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 to step 1) in raw material in, ammonium chloride therein is obtained with a part of lime reaction To ammonia, calcium chloride, the sodium sulphate in calcium chloride and well ore deposit sea lake salt raw brine and ammonium mother liquor mixed liquor processed continues to react generation Calcium sulfate precipitation thing；Magnesium sulfate in well ore deposit sea lake salt raw brine, magnesium chloride and another part lime reaction produce calcium sulfate and Magnesium hydrate precipitate thing；
5) calcium sulfate is anti-during the sulphur removal bittern after separating calcium sulphate and magnesium hydrate precipitate thing adds soda ash, with sulphur removal bittern Refined brine and lime deposit should be obtained；
6) refined brine carries out step 1) in metathesis reaction carry out subsequent cycle produce soda ash operation.
Further, each component content is NaCl 1-360g/l, Na in the well ore deposit 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 step 2) in deamination during and the step 4) in the ammonia that obtains participate in the step 1) Middle refined brine inhales ammonia；The step 2) in deamination during the carbon dioxide recovery that obtains be used for the step 1) in ammonia salt Water is carbonized.
Further, the step 1) in obtain solid sodium bicarbonate solid sodium carbonate be converted into after calcining.
Further, the step 3) in solid ammonium chloride using lime distillation obtain for refined brine inhale ammonia ammonia And by-product calcium chloride product.
Further, the step 5) in lime deposit reclaim as raw material produce lime.
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 step 1) in metathesis reaction temperature be 15-50 DEG C；The step 2) in reaction temperature It is 55-150 DEG C.
Further, each component content is NaCl 1-360g/l, Na in the refined brine2SO40.104-55g/l；Institute Each component content is NH in stating 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 bittern4 0.1-6.0g/l。
This process well ore deposit sea lake salt bittern 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 raw material production soda ash, ammonium chloride, calcium chloride product.
The beneficial effects of the invention are as follows：Well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production of the present invention, its production process In reduce energy consumption and cost, without mother liquor discharge, sodium and chlorion theoretical recovery 100% are a kind of to solve environmental protection, section The green cleansing preparation method of making of energy emission reduction.
Brief description of the drawings
Fig. 1 is the process chart of well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production of the present invention.
Specific embodiment
As shown in figure 1, the present invention provides a kind of well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production, with well ore deposit sea lake salt Bittern is raw material, after mixing 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 thing and sulphur removal bittern, and sulphur removal bittern adds soda ash to be obtained after removing calcium ion To refined brine and lime deposit, the refined brine and ammonia, carbon dioxide separate after metathesis reaction obtaining for raw material 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 contain 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 ore deposit sea lake salt raw brine, ammonium chloride therein obtains ammonia, calcium chloride, calcium chloride and well with a part of lime reaction Sodium sulphate in ore deposit sea lake salt raw brine and ammonium mother liquor mixed liquor processed continues to react generation calcium sulfate precipitation thing；Well ore deposit sea lake salt Magnesium sulfate, magnesium chloride and another part lime reaction produce calcium sulfate and magnesium hydrate precipitate thing in raw brine；Separate sulfuric acid Calcium sulfate reaction obtains refined brine and carbon during sulphur removal bittern after calcium and magnesium hydrate precipitate thing adds soda ash, with sulphur removal bittern Sour Ca-deposit；The refined brine carries out above-mentioned metathesis reaction and carries out the operation that subsequent cycle produces soda ash.
The present invention is described in detail to be exemplified below several specific embodiments.
Embodiment 1：Take 100m3Raw material (rock salt bittern) (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 Thing and sulphur removal bittern, sulphur removal bittern add soda ash to obtain refined brine and lime deposit after removing calcium ion, refine rock salt The 276.34m obtained after bittern3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) 43 tons of solid sodium bicarbonate (NaHCO of acquisition are separated afterwards for raw material carries out metathesis reaction (30 DEG C of reaction temperature)3) 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) removing 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) it is incorporated in raw material and passes 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 3.23 tons of sodium sulphate (Na in mixing bittern2SO4) continue to react 3.09 tons of calcium sulfate (CaSO of generation4) sediment；100m3Rock salt Bittern (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 produced 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 is obtained3) reclaim the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) reclaim for ammonia Salt solution 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, CaSO46.0g/l) add 1.292 tons of soda ash (Na2CO3) with bittern in 1.642 tons of calcium sulfate (CaSO4) reaction obtain 276.34m3Refined 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 bittern (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 is refined to remove refined brine (NaCl 288g/l, Na after magnesium, sulfate radical, calcium ion2SO46.26g/l) inhale the life of ammonia subsequent cycle Produce soda ash operation；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) using lime (Ca (OH)2) distillation, then can reclaim ammonia (NH3) inhale ammonia, carbon dioxide for refined brine (CO2) reclaim for ammonial brine carbonization, 28 tons of calcium chloride (CaCl of by-product2) product；1.207 tons of calcium carbonate mud of refined brine by-product (CaCO3) it is recycled as producing the raw material of lime.
Embodiment 2：Take 100m3Raw material (sea salt bittern) (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 Thing and sulphur removal bittern, sulphur removal bittern add soda ash to obtain refined brine and lime deposit after removing calcium ion, after refining The 276.34m for arriving3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) enter for raw material Row metathesis reaction (30 DEG C of reaction temperature) separates 43 tons of solid sodium bicarbonate (NaHCO of acquisition afterwards3) 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) removing 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 276.34m3In mixing bittern 3.23 tons of sodium sulphate (Na2SO4) continue to react 3.09 tons of calcium sulfate (CaSO of generation4) sediment；100m3Sea salt bittern (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) produces 0.0210 ton of calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) precipitation Thing；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 for arriving3) reclaim the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) reclaim for ammonial brine carbonization；Separate Calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m after sediment3Sulphur removal bittern (NaCl 288g/ l、CaSO46.0g/l) add 1.292 tons of soda ash (Na2CO3) with bittern in 1.642 tons of calcium sulfate (CaSO4) reaction obtain 276.34m3Refined brine (NaCl288g/l, Na2SO46.26g/l) with 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 Bittern (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 ion2SO46.26g/l) inhale ammonia subsequent cycle production soda ash operation；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 can reclaim ammonia (NH3) inhale ammonia, carbon dioxide (CO for refined brine2) reclaim 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) be recycled as producing stone The raw material of ash.
Embodiment 3：Take 100m3Lake salt bittern (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 thing and removes with lime reaction Sulphur bittern, sulphur removal bittern adds soda ash to obtain refined brine and lime deposit after removing calcium ion, is obtained after refining 276.34m3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) answered for raw material Decomposition reaction (30 DEG C of reaction temperature) separates 43 tons of solid sodium bicarbonate (NaHCO of acquisition afterwards3) 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) removing 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 276.34m3In mixing bittern 3.23 tons of sodium sulphate (Na2SO4) continue to react 3.09 tons of calcium sulfate (CaSO of generation4) sediment；100m3Lake salt bittern (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) produces 0.0210 ton of calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) precipitation Thing；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 for arriving3) reclaim the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) reclaim for ammonial brine carbonization；Separate Calcium sulfate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m after sediment3Sulphur removal bittern (NaCl 288g/ l、CaSO46.0g/l) add 1.292 tons of soda ash (Na2CO3) with bittern in 1.642 tons of calcium sulfate (CaSO4) reaction obtain 276.34m3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with 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 ion2SO46.26g/l) inhale ammonia subsequent cycle production soda ash operation；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) adopt With lime (Ca (OH)2) distillation, then can reclaim ammonia (NH3) inhale ammonia, carbon dioxide (CO for refined brine2) reclaim for ammonia Salt solution carbonization, 28 tons of calcium chloride (CaCl of by-product2) 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 Thing and sulphur removal bittern, sulphur removal bittern add soda ash to obtain refined brine and lime deposit after removing calcium ion, after refining The 276.34m for arriving3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with ammonia (NH3), carbon dioxide (CO2) enter for raw material Row metathesis reaction (30 DEG C of reaction temperature) separates 43 tons of solid sodium bicarbonate (NaHCO of acquisition afterwards3) 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) removing 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 276.34m3In mixing bittern 3.23 tons of sodium sulphate (Na2SO4) continue to react 3.09 tons of calcium sulfate (CaSO of generation4) 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) produces 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 is obtained3) reclaim the carbon dioxide (CO obtained for refined brine suction ammonia, deamination2) reclaim for ammonia salt Water is carbonized；Separating calcium sulphate (CaSO4) and 0.0145 ton of magnesium hydroxide (Mg (OH)2) 276.34m3 sulphur removal bittern after sediment (NaCl 288g/l、CaSO46.0g/l) add 1.292 tons of soda ash (Na2CO3) with bittern in 1.642 tons of calcium sulfate (CaSO4) Reaction obtains 276.34m3Refined brine (NaCl 288g/l, Na2SO46.26g/l) with 1.207 tons of calcium carbonate (CaCO3) precipitation Thing；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 bittern (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 ion2SO46.26g/l) inhale ammonia subsequent cycle production 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) using lime (Ca (OH)2) distillation, then can reclaim ammonia (NH3) inhale ammonia, carbon dioxide (CO for refined brine2) return Receive for ammonial brine carbonization, 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 producing the raw material of lime.
Present invention process advantage is：Well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production production soda ash, ammonium chloride, chlorination Calcium product, high with major-minor product quality, 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 (10)

1. a kind of well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production, it is characterised in that it is comprised the following steps：
1) with well ore deposit sea lake salt bittern as raw material, with lime reaction with stone after mixing 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 thing and sulphur removal bittern, and sulphur removal bittern adds Enter after soda ash removes calcium ion and obtain refined brine and lime deposit, the refined brine is with ammonia, carbon dioxide for raw material enters Separated after row metathesis reaction and obtain solid sodium bicarbonate and contain ammonium chloride, sodium chloride, ammonium hydrogen carbonate, ammonium carbonate and sodium sulphate 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 contains 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 to step 1) in raw material in, ammonium chloride therein is obtained with a part of lime reaction Ammonia, calcium chloride, calcium chloride continue to react generation sulphur with the sodium sulphate in well ore deposit sea lake salt raw brine and ammonium mother liquor mixed liquor processed Sour Ca-deposit；Magnesium sulfate, magnesium chloride and another part lime reaction produce calcium sulfate and hydrogen in well ore deposit sea lake salt raw brine Magnesium oxide precipitation thing；
5) calcium sulfate reacts during the sulphur removal bittern after separating calcium sulphate and magnesium hydrate precipitate thing adds soda ash, with sulphur removal bittern To refined brine and lime deposit；
6) refined brine carries out step 1) in metathesis reaction carry out subsequent cycle produce soda ash operation.
2. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1, it is characterised in that described Each component content is NaCl 1-360g/l, Na in well ore deposit 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 ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Step 2) in deamination during and the step 4) in the ammonia that obtains participate in the step 1) in refined brine inhale ammonia；The step It is rapid 2) in deamination during the carbon dioxide recovery that obtains be used for the step 1) in ammonial brine carbonization.
4. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Step 1) in obtain solid sodium bicarbonate solid sodium carbonate be converted into after calcining.
5. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Step 3) in solid ammonium chloride using lime distillation obtain for refined brine inhale ammonia ammonia and by-product calcium chloride product.
6. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Step 5) in lime deposit reclaim as raw material produce lime.
7. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Each component content is NH in ammonium mother liquor processed4Cl 5-450g/l、Na2SO4 1-55g/l、NaCl 5-360g/l。
8. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Step 1) in metathesis reaction temperature be 15-50 DEG C；The step 2) in reaction temperature be 55-150 DEG C.
9. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Each component content is NaCl 1-360g/l, Na in refined brine2SO40.104-55g/l；Each composition contains in the deamination mother liquor It is NH to measure4Cl 5-450g/l、Na2SO4 1-55g/l、NaCl 5-360g/l。
10. well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production according to claim 1 and 2, it is characterised in that described Each component content is NaCl 1-360g/l, CaSO in sulphur removal bittern4 0.1-6.0g/l。
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CN110589857A (en) * 2019-10-29 2019-12-20 常州大学 Method for preparing alkali by using waste salt in combination manner
CN112093812A (en) * 2020-10-05 2020-12-18 湖南海联三一小苏打有限公司 Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride
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CN112850754A (en) * 2021-01-26 2021-05-28 青海盐湖工业股份有限公司 Soda ash and magnesium alkali co-production system and co-production method
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
CN113173589A (en) * 2020-11-11 2021-07-27 内蒙古兰太钠业有限责任公司 Preparation system and process method of liquid salt for alkali production
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
CN114477236A (en) * 2022-01-28 2022-05-13 江西晶昊盐化有限公司 Calcium halide purification method and pH value adjustment method
CN114956147A (en) * 2022-06-22 2022-08-30 彭赛军 Process for co-producing caustic soda and barium sulfate by using salt carrier and witherite

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CN108529652A (en) * 2018-04-16 2018-09-14 黄河三角洲京博化工研究院有限公司 A kind of industrial chlorinations sodium resource utilization process
CN110589857A (en) * 2019-10-29 2019-12-20 常州大学 Method for preparing alkali by using waste salt in combination manner
CN112093812A (en) * 2020-10-05 2020-12-18 湖南海联三一小苏打有限公司 Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride
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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
CN114477236A (en) * 2022-01-28 2022-05-13 江西晶昊盐化有限公司 Calcium halide purification method and pH value adjustment method
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
CN114956147A (en) * 2022-06-22 2022-08-30 彭赛军 Process for co-producing caustic soda and barium sulfate by using salt carrier and witherite

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