Process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings
阅读说明：本技术 一种碳铵与钙芒硝尾矿联产纯碱、硫酸钙工艺 (Process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings ) 是由 彭赛军 段小伦 潘诚良 潘成全 王宁 彭志成 于 2021-02-24 设计创作，主要内容包括：一种碳铵与钙芒硝尾矿联产纯碱、硫酸钙工艺,它包括以下步骤：1)以碳铵与步骤7)中的盐卤为原料,进行复分解反应,分离获得固体碳酸氢钠和重碱母液和少量硫酸钠；2)将该固体碳酸氢钠煅烧得到纯碱产品和二氧化碳；3)该重碱母液预热高温脱除碳酸氢铵、碳酸铵后得到氨、二氧化碳和脱氨母液；4)该脱氨母液与石灰、钙芒硝尾矿反应,得到氨、二氧化碳和除铵卤水；5)该除铵卤水与石灰、纯碱反应得到除铵精卤和钙镁泥；6)该除铵精卤与步骤2)中的二氧化碳、步骤3)中的氨、二氧化碳以及步骤4)中的氨、二氧化碳反应得到盐卤；7)该盐卤循环至步骤1)复分解反应工序。(A process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings comprises the following steps: 1) carrying out double decomposition reaction on ammonium bicarbonate and the bittern obtained in the step 7) serving as raw materials, and separating to obtain solid sodium bicarbonate, heavy alkali mother liquor and a small amount of sodium sulfate; 2) calcining the solid sodium bicarbonate to obtain a soda ash product and carbon dioxide; 3) preheating the heavy alkali mother liquor at a high temperature to remove ammonium bicarbonate and ammonium carbonate to obtain ammonia, carbon dioxide and deamination mother liquor; 4) the deamination mother liquor reacts with lime and glauberite tailings to obtain ammonia, carbon dioxide and ammonium removal brine; 5) the ammonium-removing brine reacts with lime and soda ash to obtain ammonium-removing refined brine and calcium-magnesium mud; 6) the refined ammonium-removing halide reacts with the carbon dioxide in the step 2), the ammonia and the carbon dioxide in the step 3) and the ammonia and the carbon dioxide in the step 4) to obtain bittern; 7) the bittern is recycled to the metathesis step of step 1).)
1. A process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings is characterized by comprising the following steps:
1) carrying out double decomposition reaction on ammonium bicarbonate and the bittern obtained in the step 7) serving as raw materials at the reaction temperature of 10-60 ℃ for 0.5-4 hours, and separating to obtain solid sodium bicarbonate, heavy alkali mother liquor and a small amount of sodium sulfate;
2) calcining the solid sodium bicarbonate to obtain a soda ash product and carbon dioxide;
3) preheating the heavy alkali mother liquor to 60-120 ℃ to remove ammonium bicarbonate and ammonium carbonate to obtain ammonia, carbon dioxide and deamination mother liquor;
4) the deamination mother liquor reacts with lime and glauberite tailings at the reaction temperature of 25-120 ℃ for 0.5-4 hours to obtain ammonia, carbon dioxide and ammonium removal brine;
5) the ammonium-removing brine reacts with lime and soda ash to obtain ammonium-removing refined brine and calcium-magnesium mud;
6) the refined ammonium-removing halide reacts with the carbon dioxide in the step 2), the ammonia and the carbon dioxide in the step 3) and the ammonia and the carbon dioxide in the step 4) to obtain bittern;
7) the bittern is recycled to the metathesis step of step 1).
2. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: the bittern comprises the following components in percentage by weight: NaCl 200-4HCO3 20-300g/l、Na2SO4 1-8g/l。
3. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: the heavy alkali mother liquor comprises the following components in percentage by weight: NaCl 50-200g/l, Na2SO4 1-8g/l、NH4Cl 100-250g/l。
4. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: the deamination mother liquor comprises the following components in percentage by weight: NH (NH)4Cl 100-250g/l、Na2SO4 1-10g/l、NaCl 50-200g/l。
5. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: the glauberite tailings comprise the following components in percentage by weight: na (Na)2SO4 1-99％、CaSO4 1-99％、CaCO3 1-99％、MgSO4 0.01-10％。
6. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: the ammonium-removing brine comprises the following components in percentage by weight: NaCl 200-aSO4 1-7g/l、MgSO4 0.02-10g/l。
7. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: the ammonium-removing refined brine comprises the following components in percentage by weight: NaCl 200-2SO4 1-8g/l。
8. The process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings according to claim 1, which is characterized in that: replacing the glauberite tailings with nitrate salt brine, nitrate brine, sodium sulfate decahydrate, anhydrous sodium sulfate and mixed salt of nitrate salt; ammonia and carbon dioxide are used as raw materials to replace ammonium bicarbonate.
Technical Field
The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a process for co-producing sodium carbonate and calcium sulfate from ammonium bicarbonate and glauberite tailings.
Background
Known sodium sulfate production soda ash processes include a wet method soda ash and ammonium sulfate by a Lobulan method and a mirabilite method, wherein, 1) the process comprises the following steps: the Lobulan method has the defects of poor product quality, high production cost, large labor consumption, difficult continuous operation and the like because the production process is carried out between solid phases. 2) Wet process of sodium carbonate and ammonium sulfate from mirabilite (cold process combined with alkali process): the defects that solid sodium sulfate is adopted as a raw material, the cost of the raw material is high, the electric energy consumption of freezing crystallization sodium sulfate decahydrate and ammonium bicarbonate is high, and the heat energy consumption of freezing mother liquor evaporation ammonium sulfate is high exist.
In addition, the known glauberite tailings are used as raw materials for producing sodium sulfate, 1 ton of glauberite tailings is produced as a byproduct per ton of sodium sulfate, and the open stockpiling of a large amount of glauberite tailings brings salt nitrate dust and the problem of environmental pollution caused by salt nitrate-containing wastewater generated by dissolution in rainy seasons.
Therefore, the process for producing sodium sulfate by using sodium sulfate as a raw material and glauberite tailings as a raw material has limitation in practical production.
Disclosure of Invention
In view of the above problems, the invention aims to provide a process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauber's salt tailings, which has the characteristics of reasonable process flow, cheap raw materials, comprehensive utilization of distillation waste liquid, no waste liquid discharge, capability of avoiding environment pollution caused by stockpiling of the glauber's salt tailings, good environmental benefit and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings comprises the following steps:
1) carrying out double decomposition reaction on ammonium bicarbonate and the bittern obtained in the step 7) serving as raw materials at the reaction temperature of 10-60 ℃ for 0.5-4 hours, and separating to obtain solid sodium bicarbonate, heavy alkali mother liquor and a small amount of sodium sulfate;
2) calcining the solid sodium bicarbonate to obtain a soda ash product and carbon dioxide;
3) preheating the heavy alkali mother liquor to 60-120 ℃ to remove ammonium bicarbonate and ammonium carbonate to obtain ammonia, carbon dioxide and deamination mother liquor;
4) the deamination mother liquor reacts with lime and glauberite tailings at the reaction temperature of 25-120 ℃ for 0.5-4 hours to obtain ammonia, carbon dioxide and ammonium removal brine;
5) the ammonium-removing brine reacts with lime and soda ash to obtain ammonium-removing refined brine and calcium-magnesium mud;
6) the refined ammonium-removing halide reacts with the carbon dioxide in the step 2), the ammonia and the carbon dioxide in the step 3) and the ammonia and the carbon dioxide in the step 4) to obtain bittern;
7) the bittern is recycled to the metathesis step of step 1).
Further, the bittern comprises the following components in percentage by weight: NaCl 200-4HCO3 20-300g/l、Na2SO4 1-8g/l。
Further, the content of each component in the heavy alkali mother liquor is as follows:NaCl 50-200g/l、Na2SO4 1-8g/l、NH4Cl 100-250g/l。
further, the deamination mother liquor comprises the following components in percentage by weight: NH (NH)4Cl 100-250g/l、Na2SO4 1-10g/l、NaCl 50-200g/l。
Further, the glauberite tailings comprise the following components in percentage by weight: na (Na)2SO4 1-99％、CaSO4 1-99％、CaCO31-99％、MgSO4 0.01-10％。
Further, the ammonium-removing brine comprises the following components in percentage by weight: NaCl 200-4 1-7g/l、MgSO40.02-10g/l。
Further, the ammonium-removing refined brine comprises the following components in percentage by weight: NaCl 200-2SO4 1-8g/l。
Further, the glauberite tailing substitute in the process can be nitrate halide (NaCl-Na)2SO4-H2O), nitro halide (Na)2SO4-H2O), sodium sulfate decahydrate, anhydrous sodium sulfate and nitrate mixed salt;
further, the ammonium carbonate substitute in the process of the present invention may be ammonia (NH)3) Carbon dioxide (CO)2) Producing soda ash and calcium sulfate products by using the raw materials.
The invention has the beneficial effects that: the process for co-producing the soda ash and the calcium sulfate from the ammonium bicarbonate and the glauber's salt tailings has the characteristics of reasonable process flow, cheap raw materials, comprehensive utilization of distillation waste liquid, no waste liquid discharge, capability of avoiding environment pollution caused by stockpiling of the glauber's salt tailings, good environmental benefit and the like.
Drawings
FIG. 1 is a schematic diagram of an actual process flow of the process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings.
Detailed Description
Referring to fig. 1, the invention provides a process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauber's salt tailings, which comprises the following steps:
1) carrying out double decomposition reaction on ammonium bicarbonate and the bittern obtained in the step 7) serving as raw materials at the reaction temperature of 10-60 ℃ for 0.5-4 hours, and separating to obtain solid sodium bicarbonate, heavy alkali mother liquor and a small amount of sodium sulfate;
2) calcining the solid sodium bicarbonate to obtain a soda ash product and carbon dioxide;
3) preheating the heavy alkali mother liquor to 60-120 ℃ to remove ammonium bicarbonate and ammonium carbonate to obtain ammonia, carbon dioxide and deamination mother liquor;
4) the deamination mother liquor reacts with lime and glauberite tailings at the reaction temperature of 25-120 ℃ for 0.5-4 hours to obtain ammonia, carbon dioxide and ammonium removal brine;
5) the ammonium-removing brine reacts with lime and soda ash to obtain ammonium-removing refined brine and calcium-magnesium mud;
6) the refined ammonium-removing halide reacts with the carbon dioxide in the step 2), the ammonia and the carbon dioxide in the step 3) and the ammonia and the carbon dioxide in the step 4) to obtain bittern;
7) the bittern is recycled to the metathesis step of step 1).
The present invention will be described in detail below with reference to specific examples.
Example 1: 1) 158 tons of ammonium bicarbonate (NH) are taken4HCO3) And 380m in step 7)3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) as raw materials, carrying out double decomposition reaction (reaction temperature is 30 ℃, reaction time is 1.5 hours), and separating to obtain 168 tons of solid sodium bicarbonate (NaHCO)3) And 380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) (ii) a 2) 168 tons of sodium bicarbonate (NaHCO) are added3) Calcining to obtain 106 tons of sodium carbonate (Na)2CO3) Product and carbon dioxide (CO)2)；3)380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) Preheating at high temperature (100 ℃) to remove ammonium bicarbonate (NH)4HCO3) Ammonium carbonate ((NH)4)2CO3) Obtaining ammonia (NH) after3) And (2) oxidation ofCarbon (CO)2) And 380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l)；4)380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l) with 37 tons of lime (Ca (OH)2) 200 tons of glauberite tailings (Na)2SO4 30％、CaSO4 30％、CaCO3 25％、MgSO41%, etc.) reaction (reaction temperature 100 ℃, reaction time 1.5 hours) to obtain ammonia (NH)3) Carbon dioxide (CO)2) And 380m3Ammonium-removing brine (NaCl305g/l, CaSO)4 5g/l、MgSO41g/l, etc.); 5)380m3Ammonium-removing brine (NaCl305g/l, CaSO)4 5g/l、MgSO41g/l, etc.) with lime (Ca (OH)2) Sodium carbonate (Na)2CO3) Reaction to obtain 380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) and calcium magnesium mud (containing magnesium hydroxide (Mg (OH)2) And calcium carbonate (CaCO)3))；6)380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) with carbon dioxide (CO) in step 2)2) Step 3) Ammonia (NH)3) Carbon dioxide (CO)2) And step 4) ammonia (NH)3) Carbon dioxide (CO)2) Reaction to obtain 380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.); 7)380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) is recycled to the metathesis reaction step of step 1).
Example 2: 1) 158 tons of ammonium bicarbonate (NH) are taken4HCO3) And 380m in step 7)3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) as raw materials, carrying out double decomposition reaction (reaction temperature is 30 ℃, reaction time is 1.5 hours), and separating to obtain 168 tons of solid sodium bicarbonate (NaHCO)3) And 380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) (ii) a 2) 168 tons of sodium bicarbonate are added (NaHCO3) Calcining to obtain 106 tons of sodium carbonate (Na)2CO3) Product and carbon dioxide (CO)2)；3)380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) Preheating at high temperature (100 ℃) to remove ammonium bicarbonate (NH)4HCO3) Ammonium carbonate ((NH)4)2CO3) Obtaining ammonia (NH) after3) Carbon dioxide (CO)2) And 380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l)；4)380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l) and 400 tons of glauberite tailings (Na)2SO430％、CaSO4 30％、CaCO3 25％、MgSO41% etc.), 22 tons of anhydrous sodium sulfate (Na)2SO4) The reaction (reaction temperature 100 ℃, reaction time 1.5 hours) obtains ammonia (NH)3) Carbon dioxide (CO)2) And 380m3Ammonium-removing brine (NaCl305g/l, CaSO)45g/l、MgSO41g/l, etc.); 5)380m3Ammonium-removing brine (NaCl305g/l, CaSO)4 5g/l、MgSO41g/l, etc.) with lime (Ca (OH)2) Sodium carbonate (Na)2CO3) Reaction to obtain 380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) and calcium magnesium mud (containing magnesium hydroxide (Mg (OH)2) And calcium carbonate (CaCO)3))；6)380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) with carbon dioxide (CO) in step 2)2) Step 3) Ammonia (NH)3) Carbon dioxide (CO)2) And step 4) ammonia (NH)3) Carbon dioxide (CO)2) Reaction to obtain 380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.); 7)380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) is recycled to the metathesis reaction step of step 1).
Example 3: 1) 158 tons of ammonium bicarbonate (NH) are taken4HCO3) And 380m in step 7)3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) as raw materials, carrying out double decomposition reaction (reaction temperature is 30 ℃, reaction time is 1.5 hours), and separating to obtain 168 tons of solid sodium bicarbonate (NaHCO)3) And 380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) (ii) a 2) 168 tons of sodium bicarbonate (NaHCO) are added3) Calcining to obtain 106 tons of sodium carbonate (Na)2CO3) Product and carbon dioxide (CO)2)；3)380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) Preheating at high temperature (100 ℃) to remove ammonium bicarbonate (NH)4HCO3) Ammonium carbonate ((NH)4)2CO3) Obtaining ammonia (NH) after3) Carbon dioxide (CO)2) And 380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l)；4)380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l) and 400 tons of glauberite tailings (Na)2SO430％、CaSO4 30％、CaCO3 25％、MgSO41% etc.), 50 tons of sodium sulfate decahydrate (Na)2SO4.10H2O) reaction (reaction temperature 100 ℃, reaction time 1.5 hours) to obtain ammonia (NH)3) Carbon dioxide (CO)2) And 380m3Ammonium-removing brine (NaCl305g/l, CaSO)4 5g/l、MgSO41g/l, etc.); 5)380m3Ammonium-removing brine (NaCl305g/l, CaSO)4 5g/l、MgSO41g/l, etc.) with lime (Ca (OH)2) Sodium carbonate (Na)2CO3) Reaction to obtain 380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) and calcium magnesium mud (containing magnesium hydroxide (Mg (OH)2) And calcium carbonate (CaCO)3))；6)380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) with carbon dioxide from step 2)(CO2) Step 3) Ammonia (NH)3) Carbon dioxide (CO)2) And step 4) ammonia (NH)3) Carbon dioxide (CO)2) Reaction to obtain 380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.); 7)380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) is recycled to the metathesis reaction step of step 1).
Example 4: 1) 158 tons of ammonium bicarbonate (NH) are taken4HCO3) And 380m in step 7)3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) as raw materials, carrying out double decomposition reaction (reaction temperature is 30 ℃, reaction time is 1.5 hours), and separating to obtain 168 tons of solid sodium bicarbonate (NaHCO)3) And 380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) (ii) a 2) 168 tons of sodium bicarbonate (NaHCO) are added3) Calcining to obtain 106 tons of sodium carbonate (Na)2CO3) Product and carbon dioxide (CO)2)；3)380m3Heavy alkali mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l and NH4HCO3、(NH4)2CO3) Preheating at high temperature (100 ℃) to remove ammonium bicarbonate (NH)4HCO3) Ammonium carbonate ((NH)4)2CO3) Obtaining ammonia (NH) after3) Carbon dioxide (CO)2) And 380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l)；4)380m3Deamination mother liquor (NaCl 71g/l, Na)2SO4 5.22g/l、NH4Cl 179g/l) and 400 tons of glauberite tailings (Na)2SO430％、CaSO4 30％、CaCO3 25％、MgSO41% etc.), 100 tons of nitrate mixed salt (Na)2SO450% and NaCl 50% (reaction temperature 100 ℃ C., reaction time 1.5 hours) to obtain ammonia (NH)3) Carbon dioxide (CO)2) And 380m3Ammonium-removing brine (NaCl305 g/l),CaSO4 5g/l、MgSO41g/l, etc.); 5)380m3Ammonium-removing brine (NaCl305g/l, CaSO)4 5g/l、MgSO41g/l, etc.) with lime (Ca (OH)2) Sodium carbonate (Na)2CO3) Reaction to obtain 380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) and calcium magnesium mud (containing magnesium hydroxide (Mg (OH)2) And calcium carbonate (CaCO)3))；6)380m3Refined bittern for removing ammonium (NaCl305g/l, Na)2SO45.22g/l, etc.) with carbon dioxide (CO) in step 2)2) Step 3) Ammonia (NH)3) Carbon dioxide (CO)2) And step 4) ammonia (NH)3) Carbon dioxide (CO)2) Reaction to obtain 380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.); 7)380m3Bittern (NaCl305g/l, Na)2SO45.22g/l and NH4HCO3Etc.) is recycled to the metathesis reaction step of step 1).
It should be noted that the above mentioned embodiments are only preferred embodiments of the present invention, and the purpose is to make the skilled in the art better understand the present invention, and it should not be used to limit the scope and application of the present invention, and any modification, equivalent replacement, improvement, etc. made within the spirit or principle of the present invention should be included in the protection scope of the present invention.
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