CN1016865B - Producing method of sodium carbonate - Google Patents
Producing method of sodium carbonateInfo
- Publication number
- CN1016865B CN1016865B CN 89102196 CN89102196A CN1016865B CN 1016865 B CN1016865 B CN 1016865B CN 89102196 CN89102196 CN 89102196 CN 89102196 A CN89102196 A CN 89102196A CN 1016865 B CN1016865 B CN 1016865B
- Authority
- CN
- China
- Prior art keywords
- bicarbonate
- material solution
- sodium sulfate
- ammonia
- soda ash
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
- C01D7/02—Preparation by double decomposition
Abstract
The present invention relates to a solid phase preparation method of sodium carbonate using material with sodium sulfate, such as mirabilite, etc., and solid ammonium bicarbonate as raw materials. In the method, the sodium carbonate and the byproduct ammonium sulfate are prepared by the steps of dissolution of the material with sodium sulfate, impurity removal, sieved ammonium bicarbonate addition for solid phase reaction, separation, washing, dehydration and calcination. The preparation method has the advantages of less required equipment investment, simple technology, less environmental pollution, high product yield, favorable economic benefit, and flexibility in plant scale, so the method is favorable to popularization and application.
Description
The present invention relates to prepare carbonate with double decomposition, particularly a kind of material and bicarbonate of ammonia with contains sodium sulfate such as saltcake is raw material production yellow soda ash (Na
2CO
3) method.
Up to now, adopt Solvay alkaline making process (being solvay soda process) to produce yellow soda ash both at home and abroad usually, this method is a raw material with salt (NaCl), synthetic ammonia, Wingdale.But the utilization ratio of solvay soda process NaCl only about 72-74%, in reclaiming the ammonia process, discharge as " waste liquid " by a large amount of calcium chloride.
China's application for a patent for invention CN87104642 specification sheets discloses a kind of yellow soda ash producing method.Though the production process of this method is approaching with the present invention, but this method is to be main raw material with sodium-chlor, and behind permeable reactive, carry out float glass process washing impurity-removing matter, when the mother liquor settling pool carried out discharge impurities, unreacted raw material sodium-chlor, bicarbonate of ammonia that exists in the mother liquor and the sodium bicarbonate that has generated easily were pulled away and reduce the yield of utilization ratio of raw materials and intermediates sodium bicarbonate after float glass process washing.
Above-mentioned two kinds of methods are main raw material with salt all, and along with developing rapidly of China's chemical industry, under the situation of the present salt supply shortage of China, applying just of above-mentioned two kinds of yellow soda ash working systems is affected.
Also useful at home and abroad saltcake and make main raw material production yellow soda ash without salt.Method by saltcake system yellow soda ash is leblanc process the earliest.This method is, and to be raw material with saltcake, coal dust, Wingdale produce yellow soda ash through the high-temperature fusion reaction, with the melts cooling, pulverize, leach, then leach liquor concentrated, logical CO
2Carbonization is released through the precipitation removal of impurity again, concentrates, is separated, oven dry makes yellow soda ash.Because the reaction complexity of leblanc process needs high temperature again, product is impure, and yield is low, and three-waste pollution is serious, now is eliminated.
Soviet Union scientist develops again with saltcake and coal dust and carry out high temperature (1050-1080 ℃) fusion in rotary oven, generates Na
2S inclines melt to go out, through cooling, broken, leaching, then with the logical CO of leach liquor
2NaHCO is produced in carbonization
3, make yellow soda ash through separating, calcining.This method is also because of the energy consumption height, and reaction is complicated, needs high temperature again, and three-waste pollution is serious, poor product quality and being eliminated substantially.
Afterwards Soviet Union Moscow fertilizer, the shellfish Glass Li Siji of pesticide research institute professor and its coadjutant to work out with saltcake, synthetic ammonia, Wingdale again be the method for raw material production yellow soda ash.This method at first is to make dense ammonia halogen with synthetic ammonia and saltcake, denseer ammonia halogen is squeezed into carbonating tower, goes into lime-kiln gas after purifying from the tower base pressure, generates NaHCO through carburizing reagent
3, make yellow soda ash through taking out, separate, wash, calcining.This method is except that using the saltcake instead of table salt, and other is similar with solvay process.This method technical process complexity, required equipment is many, and the investment of founding the factory is huge and huge, and in the gas-liquid phase reaction process of in carbonating tower, carrying out, ammonia and Na
+Utilization ratio 64-65% is only arranged, factory cost height, deficiency in economic performance.The crystallization of sodium bicarbonate that this method generates after the gas-liquid phase reaction is tiny, has brought very adverse factors for separation, washing and calcination process.
The objective of the invention is to overcome some weak point of above-mentioned different system yellow soda ash methods, providing a kind of can be that raw material replaces salt raw material in short supply at present with the material of contains sodium sulfate cheap and easy to get such as saltcake etc., do not need complicated technology and equipment again, production technique is simple, facility investment is little, can reduce pollution, product yield height, the production method of good in economic efficiency yellow soda ash to environment.
Purpose of the present invention can reach by following measure:
A kind of method of producing yellow soda ash is with natural saltcake, the thenardite (Na of contains sodium sulfate
2SO
4), mirabilite hydrate (Na
2SO
410H
2O), urao is mixed with contains sodium sulfate 10% to saturated material solution, again with add-on for this reason sodium sulphate content 0.3-2 solid ammonium bicarbonate doubly to be soaked into temperature be to react in 10-90 ℃ the above-mentioned material solution, make it produce sodium bicarbonate, the sodium bicarbonate that produces obtains product yellow soda ash after separation, washing, dehydration and calcining.
Below in conjunction with the detailed explanation the present invention of accompanying drawing.
Accompanying drawing is a kind of process flow diagram of the present invention.As shown in drawings, with the material dissolution of contains sodium sulfate such as natural saltcake, thenardite, mirabilite hydrate, urao and be mixed with contains sodium sulfate 10% to saturated but be preferably 25% material solution to saturated contains sodium sulfate.Being 10-90 ℃ in this material solution temperature is preferably under 50-80 ℃ the condition, be soaked in this material solution and react being sized to the solid ammonium bicarbonate of particle diameter less than 20mm, the material solution of contains sodium sulfate is infiltrated in the solid ammonium bicarbonate carry out solid state reaction, like this at the very fast generation one deck of bicarbonate of ammonia particle surface sodium bicarbonate duricrust, this layer duricrust be thickening gradually, stop the decomposition of bicarbonate of ammonia to be overflowed, thereby improved the utilization ratio of bicarbonate of ammonia.Along with the continuous infiltration to the bicarbonate of ammonia granule interior of the material solution of contains sodium sulfate, solid state reaction is constantly carried out, until making the bicarbonate of ammonia particle change into sodium bicarbonate particle.Carry out to carry out in the process intermittently carry out (also can not stir) of stirring in reaction to add fast response.Along with constantly carrying out of reaction, the temperature of reaction soln also constantly reduces, and the reduction of this solution temperature can reduce the solubleness of sodium bicarbonate in solution that reaction generates.Improve reaction yield.Generally after the bicarbonate of ammonia particle is converted into sodium bicarbonate more than 90%, be considered to react basic end, carry out separation, washing, dehydration, the calcining of sodium bicarbonate then.
The separation of sodium bicarbonate, washing, dehydration are preferably in the same equipment to be carried out, and can save facility investment like this.For example after reaction finishes, reacting rear material in the reactive tank can be moved in the solid-liquid separating equipments such as whizzer or vacuum filtration machine and separate, wash, dewater, solid sodium bicarbonate is separated with mother liquor, isolated mother liquor is put into mother liquor tank, use tap water (the most handy soft water) washing heavy sodium hydrate filter cake then, mother liquor is through the freezing impurity such as most of unreacted sodium sulfate and bicarbonate of ammonia of separating out, and concentrates after these impurity of separating out in the mother liquor are removed, and can obtain byproduct of ammonium sulfate.To can be made into heavy alkali (sodium bicarbonate) product with the present technique field after the known oven drying at low temperature technology oven dry through the weight in wet base alkali after washing, the dehydration,, can obtain the yellow soda ash product the calcining of weight in wet base alkali.
The material solution of contains sodium sulfate preferably adds solid ammonium bicarbonate again and carries out solid state reaction after the removal of impurity.
The washing water that the heavy neutralizing treatment operation of gained is come can be used for dissolving the material of contains sodium sulfate, utilize contained CO in the washing water
= 3And HCO
- 3Most of calcium, magnesium, aluminium, iron ion etc. generate carbonate and acid carbonate precipitation in ion and the material solution, its precipitation together with the water-insolubles such as silt in the material solution through sedimentation or filtering separation to reach removal of impurity purpose.
The screening of solid ammonium bicarbonate is with its cake broke, screening, and preferably selects the bicarbonate of ammonia particle of particle diameter below 20mm to use when the solid state reaction.If bicarbonate of ammonia still keeps former grain size number or do not have big caking, also can be directly used in and feed intake.
The present invention compares with the leblanc process that with saltcake, coal dust, Wingdale is raw material system yellow soda ash, not only can significantly reduce facility investment, and can improve quality index such as the whiteness of product and carbonate content.Main is with above two kinds of method system yellow soda ash will produce a large amount of waste residues, waste water (contains NaOH and Na
2S etc.) and waste gas (contain CO, CO
2, SO
2, H
2S etc.) serious environment pollution, and the present invention makes in the yellow soda ash process except that generating NaHCO
3Has only by product (NH outward,
4)
2SO
4, the three wastes have seldom reduced the pollution to environment after the by-product recovery.
The present invention is no matter compare with the ammonia alkali legal system yellow soda ash that adopts usually both at home and abroad at present, and still the system yellow soda ash method that proposes with the fertile section in above-mentioned Soviet Union Moscow, pesticide research institutes is compared, and all can economize the preparation section of deammoniation bittern, CO
2The preparation section of gas, ammonia still process, the recovery of gas, cleaning section, thus significantly reduced facility investment and operating process.In addition, more than two kinds of methods all be to react in that gas-liquid is alternate, the sodium bicarbonate crystallization of generation is tiny, brings difficulty for separation, washing and calcination process.And ammonia and Na in reaction process
+Utilization ratio 64-65% is only arranged.And the present invention adopts solid ammonium bicarbonate is soaked into and carries out solid state reaction in the material solution of contains sodium sulfate, because of the material of contains sodium sulfate is solution state, so be swift in response (even can in half hour, finish reaction), the sodium bicarbonate crystalline particle that generates is thick, be beneficial to filtration, washing, calcining, and NH
+ 4, Na
+Utilization ratio more than 90%.
All storing abundant mirabilite resource in provinces and regions such as China Shanxi, Xinjiang, Inner Mongol, Gansu, Ningxia, Shaanxi, Sichuan, add up according to pertinent data, China's saltcake reserves are only second to the Soviet Union in the world, and at present saltcake except that being used to produce Sodium sulfate anhydrous.min(99), Sodium Sulphide, major part does not obtain exploitation, more is not used for deep processing.It is the solvay soda process of raw material that yellow soda ash production is at present adopted mostly with salt.The present invention can be that raw material system yellow soda ash is alleviated the present salt of China situation in short supply with saltcake instead of table salt cheap and easy to get, and simultaneously, the abundant mirabilite resource of development and use reserves is brought benefits to the people.China's bicarbonate of ammonia output ranks first in the world, and mostly makes chemical fertilizer and uses.Because the bicarbonate of ammonia chemical property is very unstable, according to agri-scientific research department report, its crop utilization rate only has 30%.When the present invention produces yellow soda ash with saltcake and bicarbonate of ammonia, also can be converted into ammonium sulfate to bicarbonate of ammonia.Because the ammonium sulfate chemical property is stable, can improve the utilization ratio of ammonia greatly.The present invention utilizes solid ammonium bicarbonate to produce yellow soda ash, and be that bicarbonate of ammonia is looked for market the dull season that can also sell at bicarbonate of ammonia, also can not influence the output of China's chemical fertilizer because of using bicarbonate of ammonia system yellow soda ash simultaneously.
Produce 500-2000 ton yellow soda ash factory per year as designing by the present invention, the facility investment of ton alkali is only about 250 yuan, than solvay soda process year ton alkali facility investment much less.Technology of the present invention is simple, and technology is easily grasped, and the scale of founding the factory is changeable, and remarkable in economical benefits is easy to utilize.
Embodiment one.Adopt thenardite or mirabilite hydrate, add the tap water dissolving and be mixed with contains sodium sulfate 25% to saturated material solution, through clarifying tank with solution in after the impurity sedimentation, with impeller pump settled solution is squeezed into reactive tank, be heated under 50-80 ℃ the condition fragmentation at the saltcake solution temperature and to be sized to particle diameter be 0.1-6mm, consumption is that 0.7 times solid ammonium bicarbonate input of sodium sulphate content is loaded onto and carried out solid state reaction in the reactive tank of stating saltcake solution in the saltcake solution.Stirred once every 2 hours between the reaction period, stirred 15 minutes at every turn, when the solid ammonium bicarbonate more than 90% changes into sodium bicarbonate, react end.Then this reacted thick material is transferred in the whizzer, open whizzer, get rid of to no mother liquor outflow, open running water valve, flushing weight in wet base sodium hydrate filter cake 2-3 minute gets rid of to no washing water outflow again, and the weight in wet base sodium hydrate filter cake is taken out, with technology calcining well known in the art, promptly get the yellow soda ash product that contains yellow soda ash 98.1%.Mother liquor can get byproduct of ammonium sulfate through freezing concentrating after removing cold analysis thing impurity.
Embodiment two.Urao with a certain amount of natural saltcake or contains sodium sulfate increases the weight of the material solution that the next washing water dissolving of neutralizing treatment operation is mixed with contains sodium sulfate 15-25%, and with this material solution clarification 4 hours, silt in the material solution and the separation of other throw out are removed, then the above-mentioned material clear liquor behind the disgorging is squeezed in the reactive tank, be heated in the material solution temperature of this contains sodium sulfate under 25-30 ℃ the condition, it is below the 15mm that input is sized to particle diameter, add-on is that the bicarbonate of ammonia of 1.5 times of sodium sulphate contents carries out solid state reaction in the contains sodium sulfate material solution, do not stir between the reaction period, reaction finishes sodium bicarbonate is carried out in the back in the vacuum filtration machine separation, washing, dehydration, other technology is same as embodiment one.Gained yellow soda ash contains yellow soda ash 98%.
Claims (3)
1, a kind of method of producing yellow soda ash, this method comprise that the sodium bicarbonate of generation obtains product yellow soda ash after separation, washing, dehydration and calcining, it is characterized in that natural saltcake, thenardite (Na with contains sodium sulfate with sodium salt and bicarbonate of ammonia reaction
2SO
4), mirabilite hydrate (Na
2SO
410H
2O), urao is mixed with contains sodium sulfate 10% to saturated material solution, again with add-on for this reason sodium sulphate content 0.3-2 solid ammonium bicarbonate doubly to be soaked into temperature be to react in 10-90 ℃ the above-mentioned material solution, make it produce sodium bicarbonate.
2, production method according to claim 1, it is characterized in that natural saltcake, thenardite, mirabilite hydrate, urao are mixed with contains sodium sulfate 25% to saturated material solution, under this material solution temperature is 50-80 ℃ condition, will be sized to particle diameter and be soaked in this material solution less than the bicarbonate of ammonia of 20mm and react, and carry out intermittence between the reaction period and stir.
3, production method according to claim 1 and 2 is characterized in that separation, washing, the dehydration of sodium bicarbonate can be carried out in same equipment, the gained washing water are used to dissolve the material of contains sodium sulfate, utilize contained CO in the washing water
= 3And HCO
- 3Most of calcium in ion and the material solution, magnesium, aluminium, iron ion generate carbonate and acid carbonate precipitation, its precipitation together with the water-insoluble in the material solution through sedimentation or filtering separation with the removal of impurity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102196 CN1016865B (en) | 1989-04-07 | 1989-04-07 | Producing method of sodium carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102196 CN1016865B (en) | 1989-04-07 | 1989-04-07 | Producing method of sodium carbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1046142A CN1046142A (en) | 1990-10-17 |
| CN1016865B true CN1016865B (en) | 1992-06-03 |
Family
ID=4854579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89102196 Expired CN1016865B (en) | 1989-04-07 | 1989-04-07 | Producing method of sodium carbonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1016865B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428759B1 (en) * | 2000-05-02 | 2002-08-06 | Fmc Wyoming Corporation | Production of feed liquors for sodium carbonate crystallization processes |
| EP2757071B1 (en) | 2013-01-17 | 2018-05-02 | General Electric Technology GmbH | Integrated carbon dioxide removal and ammonia-soda process |
| CN104355326B (en) * | 2014-10-16 | 2017-02-15 | 中国中轻国际工程有限公司 | Thermal circulation technology of utilizing sodium sulfate solution or carrier to cogenerate sodium carbonate and ammonium sulfate |
| CN104474881B (en) * | 2014-12-02 | 2016-06-08 | 成都华西堂投资有限公司 | A kind of caprolactam that utilizes burns the method for converting waste caustic soda for sodium acid carbonate in gas cleaning |
| CN104353351B (en) * | 2014-12-02 | 2016-08-17 | 成都华西堂投资有限公司 | A kind of by converting waste caustic soda for the industrialized process for preparing of sodium bicarbonate in gas cleaning |
| CN105016362A (en) * | 2015-07-15 | 2015-11-04 | 江西省广德环保科技股份有限公司 | Method for making alkali by utilization of hydrometallurgical industrial wastewater |
| CN109437248B (en) * | 2018-11-23 | 2021-06-04 | 四川金象赛瑞化工股份有限公司 | Method for joint production of soda ash and ammonium sulfate by using mirabilite and ammonium bicarbonate as raw materials |
| CN113493214B (en) | 2020-04-08 | 2022-08-23 | 北京镜澄科技有限公司 | Novel method for preparing sodium bicarbonate and co-producing ammonium sulfate from sodium sulfate |
-
1989
- 1989-04-07 CN CN 89102196 patent/CN1016865B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046142A (en) | 1990-10-17 |
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