CN110156052A - A kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique - Google Patents

A kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique Download PDF

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Publication number
CN110156052A
CN110156052A CN201910327209.1A CN201910327209A CN110156052A CN 110156052 A CN110156052 A CN 110156052A CN 201910327209 A CN201910327209 A CN 201910327209A CN 110156052 A CN110156052 A CN 110156052A
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ammonia
liquid
calcium
calcium carbonate
nacl
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Chinese (zh)
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彭赛军
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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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • 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
    • 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
    • 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
    • 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
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2/00—Lime, magnesia or dolomite
    • C04B2/02—Lime
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Fertilizers (AREA)

Abstract

A kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique, directly using bittern water as raw material, using obtaining product soda ash and evaporated waste ammonia liquid after inhaling ammonia, carbonization, calcining and lime ammonia still process series process；Clarification obtains salt calcium liquid and waste residue after the evaporated waste ammonia liquid is concentrated by evaporation；It evaporates the salt calcium liquid to obtain sodium chloride and calcium chloride solution；The calcium chloride solution is inhaled ammonia, carbonization or ammonium hydrogen carbonate is added and reacts to obtain product calcium carbonate and liquid chlorine ammonium fertilizer；Raw material using calcium carbonate as product or circulation as production lime and carbon dioxide；Using sodium chloride circulation and stress as production soda ash raw material.The features such as production process of the present invention has raw material chloride ion, sodium ion theoretical yield 100%, and comprehensive energy consumption is low and at low cost, and calcium ion recycles, no discharging of waste liquid is the green cleansing preparation method of making for solving environmental protection, energy-saving and emission-reduction.

Description

A kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique
Technical field
The invention belongs to technical field of inorganic chemical industry, especially a kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate work Skill.
Background technique
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, high production cost, manpower consumption is big and production process carries out between solid phase, difficult In work continuously the disadvantages of.2) Sol ties up method alkaline: Sol ties up method (ammonia-soda process), and there are the low (benefits of sodium of raw material chlorination sodium utilization With rate about 75%, chlorine utilization 0%) the problem of；(containing a large amount of calcium chloride, sodium chloride, every 1 ton of production is pure for slops Alkali generates 10-12m3Discharging of waste liquid) discharge system amount is very big, and waste of resource forms new environmental pollution.3) combine legal system soda ash (cold process union soda): existing need to use solid sodium chloride for raw material, and cost of material is higher, and cold analysis salting-out crystallization ammonium chloride electric energy disappears Consumption is higher, cannot directly adopt the problem of well mine sea lake salt brine is raw material.Therefore, above-mentioned technique is applied all in actual production There is limitation.
Summary of the invention
The object of the present invention is to provide a kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate techniques, are with bittern water Raw material directly produces soda ash, liquid chlorine ammonium and calcium carbonate, and production process has raw material chloride ion, sodium ion theoretical yield 100%, the features such as comprehensive energy consumption is low and at low cost, and calcium ion recycles, no discharging of waste liquid.
To achieve the above object, the present invention takes following technical scheme:
A kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique, including the following steps:
1) pure using product is obtained after suction ammonia, carbonization, calcining and lime ammonia still process series process directly using bittern water as raw material Alkali and evaporated waste ammonia liquid；
2) clarification obtains salt calcium liquid and waste residue after being concentrated by evaporation the evaporated waste ammonia liquid at 50-150 DEG C；
3) the salt calcium liquid is obtained into sodium chloride and calcium chloride solution in 50-150 DEG C of evaporation；
4) calcium chloride solution is inhaled ammonia, carbonization or ammonium hydrogen carbonate is added and react to obtain product calcium carbonate and liquid chlorine ammonium Fertilizer, reaction temperature are 25-80 DEG C, and the reaction time is 1-5 hours；
5) raw material using calcium carbonate as product or circulation as production lime and carbon dioxide；
6) using sodium chloride circulation and stress as production soda ash raw material.
Further, the NaCl content in the bittern water is 300-330g/l.
Further, the evaporated waste ammonia liquid contains CaCl2 95-140g/l、NaCl 40-100g/l。
Further, the evaporated waste ammonia liquid also contains CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3。
Further, each component content is CaCl in the salt calcium liquid2 252-350g/l、NaCl 121-131g/l。
Further, each component content is CaCl in the calcium chloride solution2 652-1151g/l、NaCl 7.31-27g/ l。
Further, each component content is NH in the liquid chlorine ammonium fertilizer4Cl 628-1109g/l、NaCl 7.31- 27g/l。
Further, bittern water of the present invention can also be NaCl-H2O (such as caustic soda light salt brine fine), Na2SO4-H2O (Ru Shishui Saltcake), NaCl-Na2SO4-H2O (such as Galuber's salt type brine), NaCl-CaSO4-H2O (such as calcium type brine) system is raw material, is produced pure Alkali, liquid chlorine ammonium, calcium carbonate product.
The beneficial effects of the present invention are: production process of the present invention has raw material chloride ion, sodium ion theoretical yield 100%, the features such as comprehensive energy consumption is low and at low cost, and calcium ion recycles, no discharging of waste liquid is to solve environmental protection, energy conservation The green cleansing preparation method of making of emission reduction.
Detailed description of the invention
Fig. 1 is the process flow diagram of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique of the present invention.
Specific embodiment
Being exemplified below several specific embodiments, the present invention is described in detail, however it is not limitation of the present invention.
As shown in Figure 1, the present invention provides a kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique, directly with bittern Water is raw material, using obtaining product soda ash and evaporated waste ammonia liquid after inhaling ammonia, carbonization, calcining and lime ammonia still process series process；By the steaming Clarification obtains salt calcium liquid and waste residue after ammonia waste liquid is concentrated by evaporation；It evaporates the salt calcium liquid to obtain sodium chloride and calcium chloride solution；It will The calcium chloride solution inhales ammonia, carbonization or ammonium hydrogen carbonate is added and reacts to obtain product calcium carbonate and liquid chlorine ammonium fertilizer；By carbonic acid Raw material of the calcium as product or circulation as production lime and carbon dioxide；Sodium chloride circulation and stress is former as production soda ash Material.
Embodiment 1: 100m is taken3Bittern water (NaCl 300g/l) is raw material with 16.41 tons of circulation and stress salt, using suction 32.82 tons of soda ash of product and 328.2m are obtained after the processes such as ammonia, carbonization, calcining and lime ammonia still process3Evaporated waste ammonia liquid (CaCl2 134g/ L, NaCl 50g/l and a small amount of CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng)；By 328.2m3Evaporated waste ammonia liquid (CaCl2134g/l, NaCl 50g/l and a small amount of CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng) evaporation (steaming Hair 125 DEG C of temperature) concentration after clarification obtain 131.28m3Salt calcium liquid (CaCl2335g/l, NaCl 125g/l) and waste residue is (mainly Containing CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng)；By 131.28m3Salt calcium liquid (CaCl2 335g/l、NaCl 125g/l) evaporation (75 DEG C of evaporating temperature) obtains 16.41 tons of sodium chloride (NaCl) and 44.27m3Calcium chloride solution (CaCl2 993.38g/l,NaCl 13.64g/l)；By 44.27m3Calcium chloride solution (CaCl2993.38g/l, NaCl 13.64g/l) it inhales Ammonium hydrogen carbonate (NH is added in ammonia, carbonization4HCO3) reaction (30 DEG C of reaction temperature, 3.5 hours reaction time) obtain product 25.86 Ton calcium carbonate (CaCO3) and 44.27m3Liquid chlorine ammonium (NH4Cl 957.26g/l, NaCl 13.64g/l) fertilizer；By 25.86 Ton calcium carbonate (CaCO3) be used as product or circulation as 14.48 tons of lime (CaO) of production and carbon dioxide (CO2) raw material；It will 16.41 tons of sodium chloride (NaCl) circulation and stress are as production soda ash (Na2CO3) raw material.
Embodiment 2: 100m is taken3Bittern water (NaCl 330g/l) is raw material with 18.05 tons of circulation and stress salt, using suction 36.10 tons of soda ash of product and 361m are obtained after the processes such as ammonia, carbonization, calcining and lime ammonia still process3Evaporated waste ammonia liquid (CaCl2 134g/l、 NaCl 50g/l and a small amount of CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng)；By 361m3Evaporated waste ammonia liquid (CaCl2134g/l, NaCl 50g/l and a small amount of CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng) evaporation (steaming Hair 125 DEG C of temperature) concentration after clarification obtain 144.41m3Salt calcium liquid (CaCl2335g/l, NaCl 125g/l) and waste residue is (mainly Containing CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng)；By 144.41m3Salt calcium liquid (CaCl2 335g/l、NaCl 125g/l) evaporation (75 DEG C of evaporating temperature) obtains 18.05 tons of sodium chloride (NaCl) and 48.70m3 calcium chloride solution (CaCl2 993.38g/l,NaCl 13.64g/l)；By 48.70m3Calcium chloride solution (CaCl2993.38g/l, NaCl 13.64g/l) it inhales Ammonium hydrogen carbonate (NH is added in ammonia, carbonization4HCO3) reaction (30 DEG C of reaction temperature, 3.5 hours reaction time) obtain product 28.45 Ton calcium carbonate (CaCO3) and 48.70m3Liquid chlorine ammonium (NH4Cl 957.26g/l, NaCl 13.64g/l) fertilizer；By 28.45 Ton calcium carbonate (CaCO3) be used as product or circulation as 15.93 tons of lime (CaO) of production and carbon dioxide (CO2) raw material；It will 18.05 tons of sodium chloride (NaCl) circulation and stress are as production soda ash (Na2CO3) raw material.
Embodiment 3: 100m is taken3Bittern water (NaCl 330g/l) is raw material with 18.05 tons of circulation and stress salt, using suction 36.10 tons of soda ash of product and 361m are obtained after the processes such as ammonia, carbonization, calcining and lime ammonia still process3Evaporated waste ammonia liquid (CaCl2 134g/l、 NaCl 50g/l and a small amount of CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng)；By 361m3Evaporated waste ammonia liquid (CaCl2134g/l, NaCl 50g/l and a small amount of CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng) evaporation (steaming Hair 100 DEG C of temperature) concentration after clarification obtain 156.19m3Salt calcium liquid (CaCl2309.72g/l, NaCl 116.73g/l) and waste residue (mainly contain CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3Deng)；By 156.19m3Salt calcium liquid (CaCl2 309.72g/l, NaCl 116.73g/l) evaporation (75 DEG C of evaporating temperature) obtain 18.05 tons of sodium chloride (NaCl) and 48.70m3Chlorine Change calcium solution (CaCl2993.38g/l,NaCl 13.64g/l)；By 48.70m3Calcium chloride solution (CaCl2 993.38g/l、 NaCl 13.64g/l) it inhales ammonia, carbonization or ammonium hydrogen carbonate (NH is added4HCO3) (30 DEG C of reaction temperature, reaction time 3.5 are small for reaction When) obtain 28.45 tons of calcium carbonate (CaCO of product3) and 48.70m3Liquid chlorine ammonium (NH4Cl 957.26g/l、NaCl 13.64g/l) fertilizer；By 28.45 tons of calcium carbonate (CaCO3) as product or circulation as production 15.93 tons of lime (CaO) and The raw material of carbon dioxide (CO2)；Using 18.05 tons of sodium chloride (NaCl) circulation and stress as production soda ash (Na2CO3) raw material.
Production process of the present invention has raw material chloride ion, sodium ion theoretical yield 100%, and comprehensive energy consumption is low and cost Low, the features such as calcium ion recycles, no discharging of waste liquid is the green cleansing preparation method of making for solving environmental protection, energy-saving and emission-reduction.
The above described is only a preferred embodiment of the present invention, not making in any form to structure of the invention Limitation.Any simple modification, equivalent change and modification to the above embodiments according to the technical essence of the invention, In the range of still falling within technical solution of the present invention.

Claims (8)

1. a kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique, characterized in that it comprises the following steps:
1) directly using bittern water as raw material, using inhale obtain after ammonia, carbonization, calcining and lime ammonia still process series process product soda ash and Evaporated waste ammonia liquid；
2) clarification obtains salt calcium liquid and waste residue after being concentrated by evaporation the evaporated waste ammonia liquid at 50-150 DEG C；
3) the salt calcium liquid is obtained into sodium chloride and calcium chloride solution in 50-150 DEG C of evaporation；
4) calcium chloride solution is inhaled ammonia, carbonization or ammonium hydrogen carbonate is added and react to obtain product calcium carbonate and liquid chlorine ammonium fertilizer Material, reaction temperature are 25-80 DEG C, and the reaction time is 1-5 hours；
5) raw material using calcium carbonate as product or circulation as production lime and carbon dioxide；
6) using sodium chloride circulation and stress as production soda ash raw material.
2. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 1 and calcium carbonate technique, it is characterised in that: the salt NaCl content in brine is 300-330g/l.
3. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 1 and calcium carbonate technique, it is characterised in that: the steaming Ammonia waste liquid contains CaCl2 95-140g/l、NaCl 40-100g/l。
4. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 3 and calcium carbonate technique, it is characterised in that: the steaming Ammonia waste liquid also contains CaSO4、CaCO3、Mg(OH)2、SiO2、CaO、Fe2O3、Al2O3。
5. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 1 and calcium carbonate technique, it is characterised in that: the salt Each component content is CaCl in calcium liquid2 252-350g/l、NaCl 121-131g/l。
6. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 1 and calcium carbonate technique, it is characterised in that: the chlorine Changing each component content in calcium solution is CaCl2 652-1151g/l、NaCl 7.31-27g/l。
7. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 1 and calcium carbonate technique, it is characterised in that: the liquid Each component content is NH in body ammonium chloride fertilizer4Cl 628-1109g/l、NaCl 7.31-27g/l。
8. ammonia alkali coproduction liquid chlorine ammonium fertilizer according to claim 1 and calcium carbonate technique, it is characterised in that: the salt Brine is NaCl-H2O、Na2SO4-H2O、NaCl-Na2SO4-H2O、NaCl-CaSO4-H2O system brine.
CN201910327209.1A 2019-04-23 2019-04-23 A kind of ammonia alkali coproduction liquid chlorine ammonium fertilizer and calcium carbonate technique Withdrawn CN110156052A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
徐学波: ""从纯碱厂蒸氨废液中回收CaCl2、NaCl的设想"", 《化学工业与工程技术》 *
李国庭等: ""氯化钙废液制备高纯碳酸钙副产工业氯化铵新工艺"", 《化工科技》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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Application publication date: 20190823