CN106082281A - Process with sodium sulfate preparing soda - Google Patents
Process with sodium sulfate preparing soda Download PDFInfo
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- CN106082281A CN106082281A CN201610424219.3A CN201610424219A CN106082281A CN 106082281 A CN106082281 A CN 106082281A CN 201610424219 A CN201610424219 A CN 201610424219A CN 106082281 A CN106082281 A CN 106082281A
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- ammonia
- sodium sulfate
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- mother solution
- chloride
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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
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to the process of a kind of sodium sulfate preparing soda, in former ammonia-sode process anhydrous sodium carbonate process, after the clarified slagging-off of mother solution after ammonia still process, distilled ammonia liquid temperature is controlled 30 65 DEG C of stirrings, according to the content of calcium chloride, add 1～1.1mol sodium sulfate reaction according to 1mol calcium chloride and generate sodium chloride and Gypsum Fibrosum (CaSO4·2H2O) precipitation, after filtration, mother solution prepares unsaturated primary brine, completes follow-up ammonia-soda process flow process.The present invention is with sodium sulfate as raw material, with chloride ion and ammonia as intermediary, it is achieved resource circulation utilization, reduces the method that waste water produces, it appears particularly significant.The present invention can reduce the generation of soda manufacture process garbage, and system can use sodium sulfate or Natrii Sulfas raw ore as raw materials for production, reduces enterprise water use amount and the outer discharge capacity of waste water, reduces and produce solid waste, improve the economic benefit of enterprise.
Description
Technical field
The invention belongs to basic industry.For using the ammonia-soda process soda manufacture technique with sodium chloride as raw material, particularly
Relate to alkali producing process replaces the process using sodium sulfate preparing soda of sodium chloride with sodium sulfate for primary raw material.
Background technology
Existing ammonia-soda process soda manufacture technique, with sodium chloride for sodium primary raw material, its main processes is shown in Fig. 3, and
Sodium chloride and sodium sulfate belong to association salt mine mostly, and sodium sulfate cannot be obtained by existing ammonia alkali process always, sulfur
Acid sodium is processed as refuse in alkaline enterprise, simultaneously during the ammonia-soda process with sodium chloride as raw materials for production, produces
Given birth to substantial amounts of waste water, salt runs off and causes environmental pollution.
Summary of the invention
The present invention provides the process of a kind of sodium sulfate preparing soda, with sodium sulfate as primary raw material, subtracts in large quantities
Few waste water generation amount and new water usage amount, and improve the utilization rate of raw material.
The technical solution of the present invention is: the process of a kind of sodium sulfate preparing soda, ammonia-sode process anhydrous sodium carbonate process
In, after the clarified slagging-off of distilled ammonia liquid, distilled ammonia liquid comprises sodium chloride 40～70g/l, calcium chloride 90～160g/l, calcium sulfate
2～8g/l, calcium hydroxide 1～4g/l, distilled ammonia liquid temperature is controlled 30-65 DEG C of stirring, according to the content of calcium chloride, according to
1mol calcium chloride adds 1～1.1mol sodium sulfate reaction and generates sodium chloride and Gypsum Fibrosum (CaSO4·2H2O) precipitation, mother solution after filtration
Preparing unsaturated primary brine, primary brine adds sodium chloride and prepares saturated crude brine, is used for producing suction ammonia after refined, after inhaling ammonia
Being cooled to 15～35 DEG C through carbon dioxide carbonization heat exchange, sodium bicarbonate saturated crystallization separates out, and filters the heated calcining of sodium bicarbonate
Decompose and produce sodium carbonate.The mother solution that sodium bicarbonate filters is heated to 80～100 DEG C, and mother solution is sent into and added alkali ash disposal tank addition hydroxide
Calcium emulsion, after reaction thoroughly, ammonia still ammonia still process sent into by clear liquid, is passed through steam bottom ammonia still, and the ammonia of generation is collected and is cooled to
40～60 DEG C are used for inhaling saline ammonia, add sodium sulfate and carry out natridization reaction, be used for producing unsaturation after the mother solution clarification after ammonia still process
Crude brine.
10～30% distilled ammonia liquid process after qualified discharge or be used for produce calcium chloride or concentrate after reuse, residue ammonia still process is female
Add sodium sulfate after liquid clarification and carry out natridization reaction, be used for producing unsaturated crude brine.
The present invention is with sodium sulfate as raw material, in the case of existing equipment need not do big change, it is achieved resources circulation profit
With, reduce waste water and produce, it appears be particularly significant.The present invention not only solves the problem of sodium sulfate resource, decreases useless simultaneously
The problem of water exhaust emission, also greatly reduces the operating cost of enterprise, improves the benefit of enterprise, is the in-depth of sodium sulfate simultaneously
Utilize and a new approach is provided.The present invention can reduce the generation of soda manufacture process garbage, and system can use sulphuric acid
Sodium or Natrii Sulfas raw ore, as raw materials for production, reduce enterprise water use amount and the outer discharge capacity of waste water, reduce and produce solid waste, improve the warp of enterprise
Ji benefit.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 process flow diagram.
Fig. 2 is natridization reaction system structure schematic diagram of the present invention.
Fig. 3 is existing ammonia-soda process soda manufacture process flow diagram.
Detailed description of the invention
A kind of process of sodium sulfate preparing soda, its specific embodiment is:
With sodium sulfate, limestone as main material, chloride ion and ammonia are as the intermediary in technical process, and major product is carbon
Acid sodium and Gypsum Fibrosum.
On the basis of existing ammonia-soda process system, increase sodium sulfate and the natridization reaction of calcium chloride and Gypsum Fibrosum filters and divides
From, it is achieved the process being raw material production soda with sodium sulfate.Main by-product has Gypsum Fibrosum (CaSO4。2H2O)。
Natridization reaction equation:
Na2SO4+CaCl2+2H2O=2NaCl+CaSO4.2H2O ↓ (precipitation)
Suction ammonia carburizing reagent equation:
NaCl+NH3+H2O+CO2=NaHCO3+NH4Cl
Deamination reaction equation:
2NH4Cl+Ca(OH)2=2NH3+2H2O+CaCl2
In ammonia-sode process anhydrous sodium carbonate process, after distilled ammonia liquid clarification slagging-off, middle main component see table:
Unit g/L
| Title | NaCl | CaCl<sub>2</sub> | CaSO<sub>2</sub> | Ca(OH)<sub>2</sub> |
| Weight g | 40-70 | 90-160 | 2-8 | 1-4 |
In ammonia-sode process anhydrous sodium carbonate process, after the clarified slagging-off of distilled ammonia liquid, control to stir at 30-65 DEG C by distilled ammonia liquid temperature
Mix, according to the content of calcium chloride, add the reaction of 1-1.1mol sodium sulfate according to 1mol calcium chloride and generate sodium chloride and Gypsum Fibrosum
(CaSO4。2H2O) precipitation, after filtration, mother solution prepares unsaturated primary brine, and primary brine adds sodium chloride and prepares saturated crude brine,
After refined, it be used for producing saturated ammonia saline, be cooled to 15-35 DEG C through carbon dioxide carbonization heat exchange after saturated ammonia saline, bicarbonate
Sodium saturated crystallization separates out, and filters the heated calcining and decomposing of sodium bicarbonate and produces sodium carbonate.Mother solution after sodium bicarbonate filters heats
To 80-100 DEG C, mother solution is sent into and is added alkali tank, adds calcium hydroxide emulsion, and after question response is thorough, supernatant sends into ammonia still ammonia still process,
Adding steam bottom ammonia still, the ammonia collection of generation is cooled to 40～60 DEG C and inhales ammonia for saturated brine, and 10～30% steam
Reuse after concentrating after qualified discharge or be used for produces calcium chloride after ammonia mother liquid disposal, adds sodium sulfate after residue distilled ammonia liquid clarification
Carry out natridization reaction, be used for producing unsaturated crude brine.
The natridization reaction implementation process of the present invention is as follows:
In ammonia-sode process anhydrous sodium carbonate process, after the clarified slagging-off of mother solution after ammonia still process, mother solution send natridization reaction pond 1, reaction controlling
At 30-65 DEG C, stirring adds sodium sulfate, is sent from scheming 3 centrifugation with pump 2 after reaction thoroughly, and Gypsum Fibrosum is used for making Building wood
Material, centrifuge mother liquor flows into cache pool 4, is sending dissolved salt pond 6 to produce saturated aqueous common salt through pump 5, then sending salt refining car through pump 7
Between, complete follow-up ammonia-soda process flow process.
As a example by certain alkali factory, by producing 1000000 tons of soda per year, use sodium sulfate economic benefit relative to sodium chloride com-parison and analysis.
1. year reduce new water consumption about 7,000,000 m3, save 63,000,000 yuan.
2. row side 7,000,000 m outside year minimizing brine waste3, reduce waste water processing cost 140,000,000 yuan.
3. reduce the consumption of 1,200,000 tons of industrial chlorinations sodium, consume 1,900,000 tons of Natrii Sulfas waste material.
4. improve the utilization rate 20% of salt, conservation expense 67,200,000 yuan
5. produce high purity plaster 1,200,000 tons, produce economic benefit 60,000,000 yuan.
Generation economic benefit is added up to be roughly equal to 330,200,000 yuan.
Therefore, this invention has great social environment benefit and economic worth.
Claims (2)
1. the process with sodium sulfate preparing soda, it is characterised in that: the mother solution in ammonia-sode process anhydrous sodium carbonate process, after ammonia still process
After clarified slagging-off, distilled ammonia liquid comprises sodium chloride 40～70g/l, calcium chloride 90～160g/l, calcium sulfate 2～8g/l, hydrogen
Calcium oxide 1～4g/l, controls 30-65 DEG C of stirring, according to the content of calcium chloride, according to 1mol calcium chloride by distilled ammonia liquid temperature
Add 1～1.1mol sodium sulfate reaction and generate sodium chloride and Gypsum Fibrosum (CaSO4·2H2O) precipitation, after filtration, mother solution prepares unsaturation
Primary brine, primary brine adds sodium chloride and prepares saturated crude brine, is used for producing suction ammonia, through carbon dioxide after suction ammonia after refined
Carbonization heat exchange is cooled to 15～35 DEG C, and sodium bicarbonate saturated crystallization separates out, the heated calcining and decomposing of sodium bicarbonate being filtrated to get
Produce sodium carbonate.The mother solution that sodium bicarbonate filters is heated to 80～100 DEG C, and mother solution is sent into and added alkali ash disposal tank, adds calcium hydroxide
Emulsion, after question response is abundant, ammonia still ammonia still process sent into by clear liquid, adds steam bottom ammonia still, and the ammonia that ammonia still process produces is collected
After, it is cooled to 40～60 DEG C and inhales ammonia for saturated brine, add sodium sulfate after the mother solution clarification after ammonia still process and carry out natridization reaction, use
In producing unsaturated crude brine.
The process of a kind of sodium sulfate preparing soda the most as claimed in claim 1, it is characterised in that: 10%-30%'s
Distilled ammonia liquid process after qualified discharge or be used for producing calcium chloride, add sodium sulfate after the clarification of remaining distilled ammonia liquid and carry out sodium
Reaction, is used for producing unsaturated crude brine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610424219.3A CN106082281A (en) | 2016-06-14 | 2016-06-14 | Process with sodium sulfate preparing soda |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610424219.3A CN106082281A (en) | 2016-06-14 | 2016-06-14 | Process with sodium sulfate preparing soda |
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| CN106082281A true CN106082281A (en) | 2016-11-09 |
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| CN201610424219.3A Pending CN106082281A (en) | 2016-06-14 | 2016-06-14 | Process with sodium sulfate preparing soda |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200337A (en) * | 2017-05-25 | 2017-09-26 | 中国中轻国际工程有限公司 | A kind of bittern of salt made from earth containing a comparatively high percentage of sodium chloride containing sodium bicarbonate production soda ash technique |
| CN107758700A (en) * | 2017-11-15 | 2018-03-06 | 陕西科原环保节能科技有限公司 | With the process of sodium sulphate preparing soda |
| CN109354038A (en) * | 2018-10-24 | 2019-02-19 | 湖北云应矿业技术开发有限公司 | A kind of saline and alkaline joint preparation process based on ammonia-soda process |
| CN109384250A (en) * | 2018-11-20 | 2019-02-26 | 黄河三角洲京博化工研究院有限公司 | A method of mixing sodium salt direct utilization |
| CN112520762A (en) * | 2020-12-08 | 2021-03-19 | 中国中轻国际工程有限公司 | Process for producing soda ash from nitrate mixed salt and soda ash production waste liquid and comprehensive utilization |
| CN113830953A (en) * | 2021-10-13 | 2021-12-24 | 烟台金正环保科技有限公司 | Comprehensive utilization system and method for seawater desalination concentrated water |
| CN114524559A (en) * | 2022-01-21 | 2022-05-24 | 国能龙源环保有限公司 | Treatment system and treatment method for resource utilization of salt separation evaporation crystallization mother liquor |
| CN117682539A (en) * | 2024-02-04 | 2024-03-12 | 北京康仑循环科技有限公司 | Method for producing sodium carbonate and high-strength gypsum by using calcium carbonate and sodium sulfate as raw materials |
Citations (3)
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| CN1297847A (en) * | 2000-12-06 | 2001-06-06 | 化学工业部连云港设计研究院 | Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid |
| CN1814548A (en) * | 2005-12-26 | 2006-08-09 | 徐贵义 | Non-waste-emission ammonia-sode process anhydrous sodium carbonate process |
| CN104556155A (en) * | 2014-12-25 | 2015-04-29 | 唐山三友化工股份有限公司 | Method for producing sodium carbonate by utilizing chlor-alkali ammonia-alkali tailings |
-
2016
- 2016-06-14 CN CN201610424219.3A patent/CN106082281A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297847A (en) * | 2000-12-06 | 2001-06-06 | 化学工业部连云港设计研究院 | Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid |
| CN1814548A (en) * | 2005-12-26 | 2006-08-09 | 徐贵义 | Non-waste-emission ammonia-sode process anhydrous sodium carbonate process |
| CN104556155A (en) * | 2014-12-25 | 2015-04-29 | 唐山三友化工股份有限公司 | Method for producing sodium carbonate by utilizing chlor-alkali ammonia-alkali tailings |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200337A (en) * | 2017-05-25 | 2017-09-26 | 中国中轻国际工程有限公司 | A kind of bittern of salt made from earth containing a comparatively high percentage of sodium chloride containing sodium bicarbonate production soda ash technique |
| CN107200337B (en) * | 2017-05-25 | 2019-05-07 | 中国中轻国际工程有限公司 | A kind of brine of salt made from earth containing a comparatively high percentage of sodium chloride containing sodium bicarbonate production soda ash technique |
| CN107758700A (en) * | 2017-11-15 | 2018-03-06 | 陕西科原环保节能科技有限公司 | With the process of sodium sulphate preparing soda |
| CN109354038A (en) * | 2018-10-24 | 2019-02-19 | 湖北云应矿业技术开发有限公司 | A kind of saline and alkaline joint preparation process based on ammonia-soda process |
| CN109384250A (en) * | 2018-11-20 | 2019-02-26 | 黄河三角洲京博化工研究院有限公司 | A method of mixing sodium salt direct utilization |
| CN112520762A (en) * | 2020-12-08 | 2021-03-19 | 中国中轻国际工程有限公司 | Process for producing soda ash from nitrate mixed salt and soda ash production waste liquid and comprehensive utilization |
| CN113830953A (en) * | 2021-10-13 | 2021-12-24 | 烟台金正环保科技有限公司 | Comprehensive utilization system and method for seawater desalination concentrated water |
| CN114524559A (en) * | 2022-01-21 | 2022-05-24 | 国能龙源环保有限公司 | Treatment system and treatment method for resource utilization of salt separation evaporation crystallization mother liquor |
| CN117682539A (en) * | 2024-02-04 | 2024-03-12 | 北京康仑循环科技有限公司 | Method for producing sodium carbonate and high-strength gypsum by using calcium carbonate and sodium sulfate as raw materials |
| CN117682539B (en) * | 2024-02-04 | 2024-04-19 | 北京康仑循环科技有限公司 | Method for producing sodium carbonate and high-strength gypsum by using calcium carbonate and sodium sulfate as raw materials |
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Application publication date: 20161109 |
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