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CN112093812A - Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride - Google Patents

Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride Download PDF

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Publication number
CN112093812A
CN112093812A CN202011067254.7A CN202011067254A CN112093812A CN 112093812 A CN112093812 A CN 112093812A CN 202011067254 A CN202011067254 A CN 202011067254A CN 112093812 A CN112093812 A CN 112093812A
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parts
ammonium chloride
brine
mixed solution
mother liquor
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Inventor
周小平
周游
李业泳
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Hunan Hlsy Sodium Bicarbonate Co ltd
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Hunan Hlsy Sodium Bicarbonate Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00Carbonates of sodium, potassium or alkali metals in general
    • C01D7/22Purification
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/16Halides of ammonium
    • C01C1/164Ammonium chloride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Fertilizers (AREA)
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Abstract

The invention discloses a cyclic manufacturing method for co-producing ammonium chloride with sodium bicarbonate, which comprises the following steps: s101, preparing a mother solution, wherein the mother solution is prepared from the following raw materials: mixing and stirring the raw materials with ammonium chloride, salt, sodium bicarbonate, water and brine for 10-16min at the rotation speed of 200-; s102, heating the mother liquor to 30-40 ℃, adding solid ammonium bicarbonate into the heated mother liquor, mixing and stirring the mixture for 5-10min at the rotation speed of 230-; according to the invention, the content of free ammonium in the baking soda mother liquor is controlled by consuming hydrochloric acid, the process is simple, the production cost is low, large-scale auxiliary equipment and machines are not needed, baking soda and ammonium chloride can be deeply extracted by two times of resolution, so that the yield of baking soda and ammonium chloride is increased, the processed mother liquor can be recycled, the waste of resources is reduced, and the environmental pollution caused by direct discharge is avoided.

Description

Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride
Technical Field
The invention relates to the technical field of ammonium chloride manufacturing, in particular to a circular manufacturing method for co-production of baking soda and ammonium chloride.
Background
It is known that during the production process of co-producing ammonium chloride by using sodium bicarbonate prepared by double decomposition method, the separated sodium bicarbonate mother liquor contains magnesium chloride, magnesium sulfate and sodium chloride, etc., wherein the sodium bicarbonate is in saturated state.
If the mother liquor is directly discharged, ammonia nitrogen can seriously pollute river water sources, and evaporation is mostly used for recovering ammonium chloride and salt in order to not discharge waste water, but the method has more defects that the total amount of ammonium chloride and sodium chloride in the mother liquor is not more than 200g/L, 5-6 tons of water are evaporated when 1 ton of ammonium chloride is recovered, 0.8 ton of coal is consumed, and in addition, the evaporated salt can hardly reach the industrial grade standard. These factors make the industrial application of the double decomposition method difficult and the economic practicality is poor.
Chinese patent CN102107889B discloses a method for processing ammonium chloride in baking soda mother liquor at normal temperature, specifically discloses a method for processing baking soda mother liquor dehydrated by a filter and a centrifuge, cooling the baking soda mother liquor to normal temperature, adding the baking soda mother liquor into an ammonia separating kettle, adding hydrochloric acid to control the content of free ammonia in the baking soda mother liquor to be less than 1.3%, and controlling the pH value to be 6.5-7.1; reacting hydrochloric acid with free ammonia and a trace amount of ammonium bicarbonate to generate ammonium chloride, and reacting hydrochloric acid with a trace amount of sodium bicarbonate to generate sodium chloride; the method has the advantages of higher hydrochloric acid consumption and higher process cost, and does not recycle the salted-out mother liquor again to cause resource waste, so the circular manufacturing method for co-producing the sodium bicarbonate and the ammonium chloride is provided.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a circular manufacturing method for co-producing sodium bicarbonate and ammonium chloride.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a circular manufacturing method for co-producing sodium bicarbonate and ammonium chloride comprises the following steps:
s101, preparing a mother solution, wherein the mother solution is prepared from the following raw materials: mixing and stirring the raw materials with ammonium chloride, salt, sodium bicarbonate, water and brine for 10-16min at the rotation speed of 200-;
s102, heating the mother liquor to 30-40 ℃, adding solid ammonium bicarbonate into the heated mother liquor, mixing and stirring the mixture for 5-10min at the rotation speed of 230-;
s103, putting the mixed solution into a cold separation crystallizer for stirring and cooling, wherein the stirring time of the mixed solution is 10-20min, the rotating speed is 1800r/min plus 1000, the temperature is reduced to 0-8 ℃, ammonium chloride is crystallized and separated out, then the obtained ammonium chloride is filtered through a sieve with 220 meshes of 150 plus materials, placed in a drying chamber for drying for 1-2h, then taken out, and kept stand and cooled to room temperature;
s104, taking the mixed solution out of the cold precipitation crystallizer, heating to 25-35 ℃, then putting the mixed solution into a salting-out kettle, simultaneously adding sodium chloride into the salting-out kettle, further crystallizing and precipitating ammonium chloride, settling to a crystal paddle taking-out port of the salting-out kettle, and returning ammonium chloride crystal paddles to the cold precipitation crystallizer in S103;
and S105, taking out the mixed solution, adding salt and brine to form new mother liquor, and returning the new mother liquor to S102 for recycling.
Preferably, in S101, the raw materials include, in parts by weight: 10-15 parts of ammonium chloride, 30-40 parts of salt, 5-10 parts of sodium bicarbonate, 50-60 parts of water and 30-40 parts of brine.
Preferably, the brine is prepared from the following raw materials: the brine comprises magnesium chloride, magnesium sulfate, sodium chloride and water, wherein the brine comprises the following components in parts by weight: 30-40 parts of magnesium chloride, 35-45 parts of magnesium sulfate, 20-30 parts of sodium chloride and 100 parts of water, wherein the preparation method of the brine comprises the following steps:
s201, mixing magnesium chloride, magnesium sulfate, sodium chloride and water, and heating to 30-40 ℃;
s202, stirring the heated mixture for 10-20min at the rotation speed of 200-250r/min to form a mixed solution;
and S203, cooling the mixed solution to room temperature to obtain brine.
Preferably, in S102, the solid ammonium bicarbonate and the mother solution are in parts by weight: 20-30 parts of solid ammonium bicarbonate and 50-60 parts of mother liquor.
Preferably, in S104, the sodium chloride and the mixed solution are in parts by weight: 10-20 parts of sodium chloride and 40-50 parts of mother liquor.
Preferably, in S105, the mixed solution, the salt and the brine in parts by weight are as follows: 50-60 parts of mixed solution, 5-10 parts of salt and 10-20 parts of brine.
Preferably, in S102, after the baking soda is filtered, the baking soda is placed in a drying chamber for drying for 0.5-1h, and then is cooled.
Preferably, in S105, after the salt and the brine are added into the mixed solution, the mixture needs to be stirred for 10-15min at a rotation speed of 220-250 r/min.
(III) advantageous effects
Compared with the prior art, the invention provides a circular manufacturing method for co-production of baking soda and ammonium chloride, which has the following beneficial effects: according to the invention, the content of free ammonium in the baking soda mother liquor is controlled by consuming hydrochloric acid, the process is simple, the production cost is low, large-scale auxiliary equipment and machines are not needed, baking soda and ammonium chloride can be deeply extracted by two times of resolution, so that the yield of baking soda and ammonium chloride is increased, the processed mother liquor can be recycled, the waste of resources is reduced, and the environmental pollution caused by direct discharge is avoided.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
Referring to fig. 1, the present invention provides a technical solution: a circular manufacturing method for co-producing sodium bicarbonate and ammonium chloride comprises the following steps:
s101, preparing a mother solution, wherein the mother solution is prepared from the following raw materials: mixing and stirring the raw materials with ammonium chloride, salt, sodium bicarbonate, water and brine for 10min at a rotation speed of 200r/min to obtain a mother liquor;
s102, heating the mother liquor to 30 ℃, adding solid ammonium bicarbonate into the heated mother liquor, mixing and stirring the mixture for 5min at the rotating speed of 230r/min to obtain baking soda, filtering the baking soda by using a 200-mesh sieve, taking out, standing and cooling to room temperature;
s103, putting the mixed solution into a cold separation crystallizer for stirring and cooling, wherein the stirring time of the mixed solution is 10-20min, the rotating speed is 1000r/min, the temperature is reduced to 2 ℃, ammonium chloride is crystallized and separated out, the obtained ammonium chloride is filtered through a 150-mesh sieve, and is placed into a drying chamber for drying for 1h, then is taken out, and is kept stand and cooled to room temperature;
s104, taking the mixed solution out of the cold precipitation crystallizer, heating to 25 ℃, then putting the mixed solution into a salting-out kettle, simultaneously adding sodium chloride into the salting-out kettle, further crystallizing and precipitating ammonium chloride, settling to a crystal paddle taking-out port of the salting-out kettle, and returning ammonium chloride crystal paddles to the cold precipitation crystallizer in S103;
and S105, taking out the mixed solution, adding salt and brine to form new mother liquor, and returning the new mother liquor to S102 for recycling.
In this embodiment, specifically: in S101, the raw materials comprise the following components in parts by weight: 10 parts of ammonium chloride, 30 parts of salt, 5 parts of sodium bicarbonate, 50 parts of water and 30 parts of brine.
In this embodiment, specifically: the brine is prepared from the following raw materials: the brine comprises magnesium chloride, magnesium sulfate, sodium chloride and water, wherein the brine comprises the following components in parts by weight: 30 parts of magnesium chloride, 35 parts of magnesium sulfate, 20 parts of sodium chloride and 100 parts of water, wherein the preparation method of the brine comprises the following steps:
s201, mixing magnesium chloride, magnesium sulfate, sodium chloride and water, and heating to 30 ℃;
s202, stirring the heated mixture for 10min at the rotating speed of 200r/min to form a mixed solution;
and S203, cooling the mixed solution to room temperature to obtain brine.
In this embodiment, specifically: in S102, the solid ammonium bicarbonate and the mother liquor are as follows according to the parts by weight: 20 parts of solid ammonium bicarbonate and 50 parts of mother liquor; ammonium bicarbonate, also called ammonium bicarbonate, is a carbonate, contains about 17.7% of nitrogen, can be used as a nitrogen fertilizer, can be decomposed into three gases of NH3, CO2 and H2O and disappears, so the ammonium bicarbonate is also called gas fertilizer, the raw materials for producing the ammonium bicarbonate are ammonia, carbon dioxide and water, the ammonium bicarbonate is colorless or light granular, platy or columnar crystal, the ammonium bicarbonate is a (sulfate) free nitrogen fertilizer, the three components of the ammonium bicarbonate are all nutrients of crops, do not contain harmful intermediate products and final decomposition products, do not affect soil quality after long-term use, and are one of the most safe nitrogen fertilizer varieties.
In this embodiment, specifically: in S104, the sodium chloride and the mixed solution are as follows according to the parts by weight: 10 parts of sodium chloride and 40 parts of mother liquor; sodium chloride, the appearance is white crystal form, its source is mainly in sea water, it is the principal ingredients of salt, it is apt to dissolve in water, glycerin, slightly dissolve in ethanol, liquid ammonia; insoluble in concentrated hydrochloric acid, slightly deliquescent in air, high stability, and may be used in producing sodium carbonate, sodium hydroxide and other chemical products.
In this embodiment, specifically: in S105, the mixed solution, the salt and the brine are as follows in parts by weight: 50 parts of mixed solution, 5 parts of salt and 10 parts of brine.
In this embodiment, specifically: in S102, after the baking soda is filtered, the baking soda is placed in a drying chamber for drying treatment, wherein the drying time is 0.5h, and then cooling is carried out.
In this embodiment, specifically: in S105, after the salt and the brine are added into the mixed solution, the mixture needs to be stirred for 10min at the rotating speed of 220 r/min.
Example two
Referring to fig. 1, the present invention provides a technical solution: a circular manufacturing method for co-producing sodium bicarbonate and ammonium chloride comprises the following steps:
s101, preparing a mother solution, wherein the mother solution is prepared from the following raw materials: mixing and stirring the raw materials with ammonium chloride, salt, sodium bicarbonate, water and brine for 14min at the rotating speed of 220r/min to obtain a mother liquor;
s102, heating the mother liquor to 35 ℃, adding solid ammonium bicarbonate into the heated mother liquor, mixing and stirring the mixture for 7min at the rotation speed of 240r/min to obtain baking soda, filtering the baking soda by using a 220-mesh sieve, taking out, standing and cooling to room temperature;
s103, putting the mixed solution into a cold separation crystallizer for stirring and cooling, wherein the stirring time of the mixed solution is 15min, the rotating speed is 1500r/min, the temperature is reduced to 5 ℃, ammonium chloride is crystallized and separated out, then the obtained ammonium chloride is filtered through a 180-mesh sieve, and is placed into a drying chamber for drying for 1.5h, then the ammonium chloride is taken out, and is kept stand and cooled to the room temperature;
s104, taking the mixed solution out of the cold precipitation crystallizer, heating to 30 ℃, then putting the mixed solution into a salting-out kettle, simultaneously adding sodium chloride into the salting-out kettle, further crystallizing and precipitating ammonium chloride, settling to a crystal paddle taking-out port of the salting-out kettle, and returning the crystal paddle of the ammonium chloride to the cold precipitation crystallizer in S103;
and S105, taking out the mixed solution, adding salt and brine to form new mother liquor, and returning the new mother liquor to S102 for recycling.
In this embodiment, specifically: in S101, the raw materials comprise the following components in parts by weight: 12 parts of ammonium chloride, 35 parts of salt, 7 parts of sodium bicarbonate, 55 parts of water and 35 parts of brine.
In this embodiment, specifically: the brine is prepared from the following raw materials: the brine comprises magnesium chloride, magnesium sulfate, sodium chloride and water, wherein the brine comprises the following components in parts by weight: 35 parts of magnesium chloride, 40 parts of magnesium sulfate, 25 parts of sodium chloride and 150 parts of water, wherein the preparation method of the brine comprises the following steps:
s201, mixing magnesium chloride, magnesium sulfate, sodium chloride and water, and heating to 35 ℃;
s202, stirring the heated mixture for 15min at the rotating speed of 220r/min to form a mixed solution;
and S203, cooling the mixed solution to room temperature to obtain brine.
In this embodiment, specifically: in S102, the solid ammonium bicarbonate and the mother liquor are as follows according to the parts by weight: 25 parts of solid ammonium bicarbonate and 55 parts of mother liquor.
In this embodiment, specifically: in S104, the sodium chloride and the mixed solution are as follows according to the parts by weight: 15 parts of sodium chloride and 45 parts of mother liquor.
In this embodiment, specifically: in S105, the mixed solution, the salt and the brine are as follows in parts by weight: 55 parts of mixed solution, 7 parts of salt and 15 parts of brine.
In this embodiment, specifically: in S102, after the baking soda is filtered, the baking soda is placed in a drying chamber for drying treatment, wherein the drying time is 1h, and then cooling is carried out.
In this embodiment, specifically: in S105, after adding the salt and the brine into the mixed solution, the mixture needs to be stirred for 12min at a rotation speed of 230 r/min.
EXAMPLE III
Referring to fig. 1, the present invention provides a technical solution: a circular manufacturing method for co-producing sodium bicarbonate and ammonium chloride comprises the following steps:
s101, preparing a mother solution, wherein the mother solution is prepared from the following raw materials: mixing and stirring the raw materials with ammonium chloride, salt, sodium bicarbonate, water and brine for 16min at the rotating speed of 230r/min to obtain a mother liquor;
s102, heating the mother liquor to 40 ℃, adding solid ammonium bicarbonate into the heated mother liquor, mixing and stirring the mixture for 10min at the rotation speed of 250r/min to obtain baking soda, filtering the baking soda by using a 250-mesh sieve, taking out, standing and cooling to room temperature;
s103, putting the mixed solution into a cold separation crystallizer for stirring and cooling, wherein the stirring time of the mixed solution is 20min, the rotating speed is 1800r/min, the temperature is reduced to 8 ℃, ammonium chloride is crystallized and separated out, then the obtained ammonium chloride is filtered through a 220-mesh sieve, and is placed into a drying chamber for drying for 2h, then the ammonium chloride is taken out, and is kept stand and cooled to the room temperature;
s104, taking the mixed solution out of the cold precipitation crystallizer, heating to 35 ℃, then putting the mixed solution into a salting-out kettle, simultaneously adding sodium chloride into the salting-out kettle, further crystallizing and precipitating ammonium chloride, settling to a crystal paddle taking-out port of the salting-out kettle, and returning the crystal paddle of the ammonium chloride to the cold precipitation crystallizer in S103;
and S105, taking out the mixed solution, adding salt and brine to form new mother liquor, and returning the new mother liquor to S102 for recycling.
In this embodiment, specifically: in S101, the raw materials comprise the following components in parts by weight: 15 parts of ammonium chloride, 40 parts of salt, 10 parts of sodium bicarbonate, 60 parts of water and 40 parts of brine.
In this embodiment, specifically: the brine is prepared from the following raw materials: the brine comprises magnesium chloride, magnesium sulfate, sodium chloride and water, wherein the brine comprises the following components in parts by weight: 40 parts of magnesium chloride, 45 parts of magnesium sulfate, 30 parts of sodium chloride and 200 parts of water, wherein the preparation method of the brine comprises the following steps:
s201, mixing magnesium chloride, magnesium sulfate, sodium chloride and water, and heating to 40 ℃;
s202, stirring the heated mixture for 20min at the rotating speed of 250r/min to form a mixed solution;
and S203, cooling the mixed solution to room temperature to obtain brine.
In this embodiment, specifically: in S102, the solid ammonium bicarbonate and the mother liquor are as follows according to the parts by weight: 30 parts of solid ammonium bicarbonate and 60 parts of mother liquor.
In this embodiment, specifically: in S104, the sodium chloride and the mixed solution are as follows according to the parts by weight: 20 parts of sodium chloride and 50 parts of mother liquor.
In this embodiment, specifically: in S105, the mixed solution, the salt and the brine are as follows in parts by weight: 60 parts of mixed solution, 10 parts of salt and 20 parts of brine.
In this embodiment, specifically: in S102, after the baking soda is filtered, the baking soda is placed in a drying chamber for drying treatment, wherein the drying time is 1h, and then cooling is carried out.
In this embodiment, specifically: in S105, after the salt and the brine are added into the mixed solution, the mixture needs to be stirred for 15min at the rotation speed of 250 r/min.
In summary, the working principle and the working process of the circular manufacturing method for co-producing the ammonium chloride by the baking soda are that when the circular manufacturing method is used, free ammonium content in baking soda mother liquor is controlled by consuming hydrochloric acid, the process is simple, the production cost is low, large-scale auxiliary equipment and machines are not needed, baking soda and ammonium chloride can be extracted deeply through twice analysis, so that the yield of the baking soda and the ammonium chloride is increased, the processed mother liquor can be recycled, the waste of resources is reduced, and the direct discharge is avoided to cause environmental pollution.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. A circular manufacturing method for co-producing ammonium chloride by baking soda is characterized in that: the method comprises the following steps:
s101, preparing a mother solution, wherein the mother solution is prepared from the following raw materials: mixing and stirring the raw materials with ammonium chloride, salt, sodium bicarbonate, water and brine for 10-16min at the rotation speed of 200-;
s102, heating the mother liquor to 30-40 ℃, adding solid ammonium bicarbonate into the heated mother liquor, mixing and stirring the mixture for 5-10min at the rotation speed of 230-;
s103, putting the mixed solution into a cold separation crystallizer for stirring and cooling, wherein the stirring time of the mixed solution is 10-20min, the rotating speed is 1800r/min plus 1000, the temperature is reduced to 0-8 ℃, ammonium chloride is crystallized and separated out, then the obtained ammonium chloride is filtered through a sieve with 220 meshes of 150 plus materials, placed in a drying chamber for drying for 1-2h, then taken out, and kept stand and cooled to room temperature;
s104, taking the mixed solution out of the cold precipitation crystallizer, heating to 25-35 ℃, then putting the mixed solution into a salting-out kettle, simultaneously adding sodium chloride into the salting-out kettle, further crystallizing and precipitating ammonium chloride, settling to a crystal paddle taking-out port of the salting-out kettle, and returning ammonium chloride crystal paddles to the cold precipitation crystallizer in S103;
and S105, taking out the mixed solution, adding salt and brine to form new mother liquor, and returning the new mother liquor to S102 for recycling.
2. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 1, is characterized in that: in S101, the raw materials comprise the following components in parts by weight: 10-15 parts of ammonium chloride, 30-40 parts of salt, 5-10 parts of sodium bicarbonate, 50-60 parts of water and 30-40 parts of brine.
3. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 2 is characterized in that: the brine is prepared from the following raw materials: the brine comprises magnesium chloride, magnesium sulfate, sodium chloride and water, wherein the brine comprises the following components in parts by weight: 30-40 parts of magnesium chloride, 35-45 parts of magnesium sulfate, 20-30 parts of sodium chloride and 100 parts of water, wherein the preparation method of the brine comprises the following steps:
s201, mixing magnesium chloride, magnesium sulfate, sodium chloride and water, and heating to 30-40 ℃;
s202, stirring the heated mixture for 10-20min at the rotation speed of 200-250r/min to form a mixed solution;
and S203, cooling the mixed solution to room temperature to obtain brine.
4. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 1, is characterized in that: in S102, the solid ammonium bicarbonate and the mother liquor are as follows according to the parts by weight: 20-30 parts of solid ammonium bicarbonate and 50-60 parts of mother liquor.
5. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 1, is characterized in that: in the step S104, the sodium chloride and the mixed solution are as follows according to the parts by weight: 10-20 parts of sodium chloride and 40-50 parts of mother liquor.
6. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 1, is characterized in that: in the S105, the mixed solution, the salt and the brine are as follows in parts by weight: 50-60 parts of mixed solution, 5-10 parts of salt and 10-20 parts of brine.
7. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 1, is characterized in that: in S102, after the baking soda is filtered, the baking soda is placed in a drying chamber for drying treatment, wherein the drying time is 0.5-1h, and then cooling is carried out.
8. The recycling manufacturing method of baking soda and ammonium chloride as well as the claim 1, is characterized in that: in S105, after the salt and the brine are added into the mixed solution, the mixture needs to be stirred, the stirring time is 10-15min, and the rotation speed is 220-250 r/min.
CN202011067254.7A 2020-10-05 2020-10-05 Cyclic manufacturing method for co-production of sodium bicarbonate and ammonium chloride Pending CN112093812A (en)

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CN106865579A (en) * 2017-02-16 2017-06-20 中国中轻国际工程有限公司 Well ore deposit sea lake salt bittern thermal cycling method ammonia integrated soda production
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CN109879297A (en) * 2019-03-25 2019-06-14 湖南裕华科技集团股份有限公司 From containing ammonium chloride, sodium chloride, ammonium hydrogen carbonate, sodium bicarbonate mother liquor in thermal method recycling product technique

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