阅读说明：本技术 一种硝盐混合盐与制碱废液生产纯碱及综合利用工艺 (Process for producing soda ash from nitrate mixed salt and soda ash production waste liquid and comprehensive utilization ) 是由 彭赛军 彭志成 于 2020-12-08 设计创作，主要内容包括：一种硝盐混合盐与制碱废液生产纯碱及综合利用工艺,包括下列步骤：1)以硝盐混合盐与制碱蒸馏废液为原料,进行复分解反应,分离得到石膏和除钙母液；2)将该除钙母液加入石灰、纯碱进行复分解反应,除去硫酸镁、硫酸钙,分离得到钙镁泥和精制液；3)将该石膏和该钙镁泥脱盐、脱水、干化综合利用为建筑砂浆材料；4)该精制液吸氨、碳酸化、石灰蒸馏、煅烧得到纯碱产品和制碱蒸馏废液；5)该制碱蒸馏废液循环至步骤1)中硝盐混合盐为原料。(A process for producing soda ash from nitrate mixed salt and soda production waste liquid and comprehensively utilizing the same comprises the following steps: 1) carrying out double decomposition reaction on nitrate mixed salt and alkali making distillation waste liquid serving as raw materials, and separating to obtain gypsum and calcium-removing mother liquid; 2) adding lime and soda ash into the calcium-removed mother liquor to perform double decomposition reaction, removing magnesium sulfate and calcium sulfate, and separating to obtain calcium-magnesium mud and refined liquor; 3) desalting, dehydrating and drying the gypsum and the calcium-magnesium mud to comprehensively utilize the gypsum and the calcium-magnesium mud as building mortar materials; 4) absorbing ammonia, carbonating, distilling lime and calcining the refined solution to obtain a soda product and a soda distillation waste solution; 5) recycling the alkali-making distillation waste liquid to the nitrate mixed salt in the step 1) as a raw material.)

1. A process for producing soda ash from nitrate mixed salt and soda production waste liquid and comprehensively utilizing the same is characterized by comprising the following steps:

1) carrying out double decomposition reaction on nitrate mixed salt and alkali making distillation waste liquid serving as raw materials at the reaction temperature of 25-70 ℃ for 0.2-5 hours, and separating to obtain gypsum and calcium-removing mother liquid;

2) adding lime and soda ash into the calcium-removed mother liquor to carry out double decomposition reaction at the temperature of 25-70 ℃ for 0.2-5 hours, removing magnesium sulfate and calcium sulfate, and separating to obtain calcium-magnesium mud and refined liquid;

3) desalting, dehydrating and drying the gypsum and the calcium-magnesium mud to comprehensively utilize the gypsum and the calcium-magnesium mud as building mortar materials;

4) absorbing ammonia, carbonating, distilling lime and calcining the refined solution to obtain a soda product and a soda distillation waste solution;

5) recycling the alkali-making distillation waste liquid to the nitrate mixed salt in the step 1) as a raw material.

2. The process for producing soda ash and comprehensively utilizing the same as claimed in claim 1, wherein the process comprises mixing the nitrate with the waste liquor of soda production: the weight contents of the components in the nitrate mixed salt are as follows: na (Na)₂SO₄ 2-97％、CaSO₄1-2％、NaCl 2-97％、MgSO₄ 0.1-1％。

3. The process for producing soda ash and comprehensively utilizing the same as claimed in claim 1, wherein the process comprises the steps of: the content of each component in the alkali-making distillation waste liquid is as follows: CaCl₂ 100-120g/l、NaCl 50-60g/l、CaO 1-10g/l。

4. The process for producing soda ash and comprehensively utilizing the same as claimed in claim 1, wherein the process comprises the steps of: the calcium removal mother liquor comprises the following components in percentage by weight: CaSO₄ 6g/l、NaCl 300-360g/l、MgSO₄ 0.1-3.0g/l。

5. The process for producing soda ash and comprehensively utilizing the same as claimed in claim 1, wherein the process comprises the steps of: the refining solution contains NaCl 300-360 g/l.

6. The process for producing soda ash and comprehensively utilizing the same as claimed in claim 1, wherein the process comprises the steps of: the calcium magnesium mud contains magnesium hydroxide and calcium carbonate.

7. The process for producing soda ash from the waste liquor of soda production and the mixed salt of nitrate according to claim 1, wherein the mixed salt of nitrate is glauberite, mirabilite, brine of nitrate, glauber salt lake, sodium sulfate decahydrate system and calcium chloride carrier.

Technical Field

The invention belongs to the technical field of inorganic chemical industry, and particularly relates to a process for producing soda ash by using nitrate mixed salt and soda ash production waste liquid and comprehensively utilizing the same.

Background

The known processes for producing the calcined soda comprise a Lobulan method, an ammonia-soda method and a cold-process combined-soda method, wherein 1) the production of the calcined soda by 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) The sodium chloride utilization rate of raw material exists in the process of preparing alkali by a Soervine method (ammonia-soda method)Low (sodium utilization rate is about 75%, chlorine utilization rate is 0%), and distillation waste liquor (containing large amount of calcium chloride and sodium chloride, and producing 9-10m for each 1 ton of soda³Waste liquid discharge) is extremely large, and new environmental pollution is generated while resources are wasted. 3) The combined method (cold-method combined alkali method) for preparing the sodium carbonate needs to adopt solid sodium chloride as a raw material, so that the cost of the raw material is higher, the electric energy consumption of cold-precipitation salting-out crystallization ammonium chloride is higher, the application range of a byproduct ammonium chloride in northern areas is small, and the like. Therefore, the above processes have limitations in practical production applications.

Disclosure of Invention

The invention aims to provide a process for producing soda ash by using mixed salt of nitrate and soda production waste liquid and comprehensive utilization, which has the characteristics of cheap raw materials, capability of producing soda ash and building mortar material products, high added values of main and auxiliary products, wide market, low comprehensive energy consumption and cost of production, closed cycle, no discharge of waste liquid and waste residue, and environment-friendly and green process.

In order to achieve the purpose, the invention adopts the following technical scheme:

a process for producing soda ash from nitrate mixed salt and soda production waste liquid and comprehensively utilizing the same comprises the following steps:

1) carrying out double decomposition reaction on nitrate mixed salt and alkali making distillation waste liquid serving as raw materials at the reaction temperature of 25-70 ℃ for 0.2-5 hours, and separating to obtain gypsum and calcium-removing mother liquid;

2) adding lime and soda ash into the calcium-removed mother liquor to carry out double decomposition reaction at the temperature of 25-70 ℃ for 0.2-5 hours, removing magnesium sulfate and calcium sulfate, and separating to obtain calcium-magnesium mud and refined liquid;

3) desalting, dehydrating and drying the gypsum and the calcium-magnesium mud to comprehensively utilize the gypsum and the calcium-magnesium mud as building mortar materials;

4) absorbing ammonia, carbonating, distilling lime and calcining the refined solution to obtain a soda product and a soda distillation waste solution;

5) recycling the alkali-making distillation waste liquid to the nitrate mixed salt in the step 1) as a raw material.

Further, the weight contents of the components in the nitrate mixed salt are as follows: na (Na)₂SO₄ 2-97％、CaSO₄ 1-2％、NaCl 2-97％、MgSO₄ 0.1-1％。

Further, the content of each component in the alkali-making distillation waste liquid is as follows: CaCl₂ 100-120g/l、NaCl 50-60g/l、CaO 1-10g/l。

Further, the calcium removal mother liquor comprises the following components in percentage by weight: CaSO₄ 6g/l、NaCl 300-360g/l、MgSO₄0.1-3.0g/l。

Further, the refining solution contains NaCl 300-360 g/l.

Further, the calcium magnesium mud contains magnesium hydroxide and calcium carbonate.

Further, the nitrate mixed salt can also be glauberite (mainly containing sodium sulfate (Na)₂SO₄、NaCl、CaSO₄、CaCO₃) Mirabilite ore (mainly containing sodium sulfate (Na)₂SO₄NaCl, and nitrate brine (mainly containing sodium sulfate (Na)₂SO₄NaCl), Natrii sulfas decahydrate (containing sodium sulfate decahydrate (Na) as main component₂SO₄·10H₂O), Miscanthus lake ore (mainly containing sodium sulfate (Na)₂SO₄) Sodium sulfate decahydrate (Na)₂SO₄·10H₂O, NaCl) system and calcium chloride carrier (mainly containing (CaCl)₂))。

The invention has the beneficial effects that: in the process for producing the soda ash by using the mixed salt of the nitrate and the waste liquid from the soda production and the comprehensive utilization process, the raw materials of the mixed salt of the nitrate and the distilled waste liquid from the soda production and the lime production are cheap, the soda ash and the building mortar material products can be produced, and the process has the characteristics of high added values of main and auxiliary products, wide market, low comprehensive energy consumption and cost of production, no waste liquid and waste residue discharge in closed cycle, environment-friendly and green process and the like.

Drawings

FIG. 1 is a schematic flow chart of the process for producing soda ash and comprehensively utilizing the waste liquor of the invention.

Detailed Description

As shown in figure 1, the invention provides a process for producing soda ash and comprehensively utilizing the same by using nitrate mixed salt and soda waste liquor, which comprises the following steps: 1) carrying out double decomposition reaction on nitrate mixed salt and alkali making distillation waste liquid serving as raw materials, and separating to obtain gypsum and calcium-removing mother liquid; 2) adding lime and soda ash into the calcium-removed mother liquor to perform double decomposition reaction, removing magnesium sulfate and calcium sulfate, and separating to obtain calcium-magnesium mud and refined liquor; 3) desalting, dehydrating and drying the gypsum and the calcium-magnesium mud to comprehensively utilize the gypsum and the calcium-magnesium mud as building mortar materials; 4) absorbing ammonia, carbonating, distilling lime and calcining the refined solution to obtain a soda product and a soda distillation waste solution; 5) recycling the alkali-making distillation waste liquid to the nitrate mixed salt in the step 1) as a raw material.

The present invention will be described in detail below with reference to specific examples.

Example 1: 118.33 tons of nitrate mixed salt (containing Na)₂SO₄ 48％、CaSO₄ 1％、NaCl 48％、MgSO₄1%) and 400m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l and CaO 1g/l) are subjected to double decomposition reaction (the reaction temperature is 25 ℃ and the reaction time is 2 hours) and then separated to obtain 44.66 tons of gypsum (containing 43.8 tons of CaSO)₄And 0.86 ton of MgSO₄) And 400m³Calcium-removing mother liquor (containing CaSO)₄ 6g/l、NaCl 312.5g/l、MgSO₄0.82 g/l); will be 400m³Adding 0.20 ton lime (Ca (OH) into the calcium removal mother liquor₂) 1.87 tons of soda ash (Na)₂CO₃) The double decomposition reaction was carried out (reaction temperature 25 ℃ C., reaction time 2 hours) and magnesium sulfate (MgSO) was removed₄) Calcium sulfate (CaSO)₄) Separating to obtain 1.92 tons of calcium-magnesium mud (containing 0.16 tons of magnesium hydroxide and 1.76 tons of calcium carbonate) and 400m³Refined solution (containing 312.5g/l NaCl); 44.66 tons of gypsum (43.8 tons of CaSO)₄And 0.86 ton of MgSO₄) And 1.92 tons of calcium-magnesium mud (containing magnesium hydroxide and calcium carbonate) is desalted, dehydrated and dried to comprehensively utilize more than 46.58 tons of building mortar materials; 400m³Refined solution (containing NaCl 312.5g/l) is ammonia absorbed, carbonated, lime distilled and calcined to obtain 114.22 tons of sodium carbonate (Na)₂CO₃) Product and 400m³Distillation waste liquor (containing CaCl) for producing alkali₂ 110g/l、NaCl 55g/l、CaO 1g/l)；400m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l NaCl 55g/l CaO 1g/l) are circulated and 118.33 tons of nitrate mixed salt (containing Na)₂SO₄ 48％、CaSO₄ 1％、NaCl 48％、MgSO₄1%) as originalAnd (5) feeding.

Example 2: 100 tons of mirabilite ore (containing Na) are taken₂SO₄ 48％、CaSO₄ 1％、NaCl 48％、MgSO₄1%) and 340m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.) are subjected to double decomposition reaction (reaction temperature is 25 ℃ and reaction time is 2 hours), and 38 tons of gypsum (containing 37.23 tons of CaSO) are separated₄And 0.77 ton MgSO₄) And 340m³Calcium-removing mother liquor (containing CaSO)₄ 6g/l、NaCl 312.5g/l、MgSO₄0.82 g/l); will be 340m³Adding 0.17 ton lime (Ca (OH) into the calcium-removing mother liquor₂) 1.59 ton of soda ash (Na)₂CO₃) The double decomposition reaction was carried out (reaction temperature 25 ℃ C., reaction time 2 hours) and magnesium sulfate (MgSO) was removed₄) Calcium sulfate (CaSO)₄) Separating to obtain 1.63 tons of calcium-magnesium mud (containing 0.14 tons of magnesium hydroxide and 1.50 tons of calcium carbonate) and 340m³Refined solution (containing 312.5g/l NaCl); 38 tons of gypsum (containing 37.23 tons of CaSO)₄And 0.77 ton MgSO₄) And 1.63 tons of calcium-magnesium mud (containing magnesium hydroxide and calcium carbonate) is desalted, dehydrated and dried to comprehensively utilize more than 39.59 tons of building mortar materials; 340m³Refined solution (containing NaCl 312.5g/l) is ammonia absorbed, carbonated, lime distilled and calcined to obtain 97.09 tons of sodium carbonate (Na)₂CO₃) Product sum 340m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.); 340m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.) and 100 tons of mirabilite ore (containing Na)₂SO₄ 48％、CaSO₄ 1％、NaCl 48％、MgSO₄1%) as raw material.

Example 3: 118.33 tons of glauberite ore (containing Na)₂SO₄ 33.6％、CaSO₄ 30％、NaCl 1％、MgSO₄1%) and 280m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.) are subjected to double decomposition reaction (reaction temperature is 25 ℃ and reaction time is 2 hours) and 67.11 tons of gypsum (containing 66.16 tons of CaSO) are separated₄And 0.95 ton of MgSO₄) And 280m³Calcium-removing mother liquor (containing CaSO)₄ 6g/l、NaCl 312.5g/l、MgSO₄ 0.82 g/l); will be 280m³Adding 0.14 ton lime (Ca (OH) into the calcium removal mother liquor₂) 1.31 ton of soda ash (Na)₂CO₃) The double decomposition reaction was carried out (reaction temperature 25 ℃ C., reaction time 2 hours) and magnesium sulfate (MgSO) was removed₄) Calcium sulfate (CaSO)₄) Separating to obtain 1.35 tons of calcium-magnesium mud (containing 0.11 tons of magnesium hydroxide and 1.24 tons of calcium carbonate) and 280m³Refined solution (containing 312.5g/l NaCl); 67.11 ton of gypsum (containing 66.16 ton of CaSO)₄And 0.95 ton of MgSO₄) And 1.35 tons of calcium-magnesium mud (containing 0.11 tons of magnesium hydroxide and 1.24 tons of calcium carbonate) are desalted, dehydrated and dried to comprehensively utilize more than 68.46 tons of building mortar materials; 280m³The refined solution (containing NaCl 312.5g/l) is ammonia-absorbed, carbonated, lime-distilled and calcined to obtain 80 tons of sodium carbonate (Na)₂CO₃) Product sum of 280m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.); 280m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.) and 118.33 tons of glauberite ore (containing Na)₂SO₄ 33.6％、CaSO₄ 30％、NaCl 1％、MgSO₄1%) as raw material.

Example 4: 118.33 tons of Miscanthus lake ore (containing Na)₂SO₄ 43.2％、CaSO₄ 1％、NaCl 4.8％、MgSO₄1%) and 360m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.) are subjected to double decomposition reaction (reaction temperature is 25 ℃ and reaction time is 2 hours) and 40.19 tons of gypsum (containing 39.42 tons of CaSO) are separated₄And 0.77 ton MgSO₄) And 360m³Calcium-removing mother liquor (containing CaSO)₄6 g/l、NaCl 312.5g/l、MgSO₄0.82 g/l); will 360m³Adding 0.18 ton lime (Ca (OH) into the calcium removal mother liquor₂) 1.78 tons of soda ash (Na)₂CO₃) The double decomposition reaction was carried out (reaction temperature 25 ℃ C., reaction time 2 hours) and magnesium sulfate (MgSO) was removed₄) Calcium sulfate (CaSO)₄) Separating to obtain 1.83 tons of calcium-magnesium mud (containing 0.14 tons of magnesium hydroxide and 1.68 tons of calcium carbonate) and 360m³Refined solution (containing 312.5g/l NaCl); 40.19 ton gypsum (containing 39.42 ton CaSO)₄And 0.77 ton MgSO₄) And 1.83 tons of calcium-magnesium mud (containing 0.14 tons of magnesium hydroxide and1.68 tons of calcium carbonate) is desalted, dehydrated and dried, and the comprehensive utilization is more than 42.02 tons of building mortar material; 360m³Refined solution (containing NaCl 312.5g/l) is ammonia absorbed, carbonated, lime distilled and calcined to obtain 102.80 tons of sodium carbonate (Na)₂CO₃) Product and 360m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.); 360m³Distillation waste liquor (containing CaCl) for producing alkali₂110g/l, NaCl 55g/l, CaO 1g/l, etc.) and 118.33 tons of Mangiferin lake ore (containing Na)₂SO₄ 43.2％、CaSO₄ 1％、NaCl 4.8％、MgSO₄1%) as raw material.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the structure of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention still fall within the scope of the technical solution of the present invention.