CN1035272A - The preparation method of active sodium carbonate - Google Patents
The preparation method of active sodium carbonate Download PDFInfo
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- CN1035272A CN1035272A CN 88107114 CN88107114A CN1035272A CN 1035272 A CN1035272 A CN 1035272A CN 88107114 CN88107114 CN 88107114 CN 88107114 A CN88107114 A CN 88107114A CN 1035272 A CN1035272 A CN 1035272A
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- drying
- sodium carbonate
- temperature
- soda ash
- yellow soda
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Abstract
With Na
2CO
310H
2The mixture of O or itself and water carries out drying in 32 ℃ below the temperature, until its crystal water content corresponding to consisting of Na
2CO
35H
2O or crystal water are lower.The drying temperature that can raise then, products therefrom has very high reactive behavior to sulfurous gas.
Description
The present invention relates to from waste gas, remove the preparation method of the used active sodium carbonate of sulfurous gas.
It is known that a kind of method for preparing active sodium carbonate is arranged, and is exactly with sodium bicarbonate (NaHCO
3) produce this product for starting raw material.Described in No. 4105744, United States Patent (USP),, in a kind of air-flow, make sodium bicarbonate carry out pyrolysis by steam partial pressure with under by the condition that temperature limited.Excellent performance with the made active anhydrous sodium carbonate of this method shows that sulfurous gas is had high reactive behavior, and the gas sweetening degree that it can reach is higher than 95%, and the average availability of the receptivity of this active sodium carbonate surpasses 90%.
There is shortcoming in the method for preparing active sodium carbonate from sodium bicarbonate, is exactly that this method consumed energy is many, and this starting raw material price height, relatively is difficult to obtain.The another kind of method of preparation carbon sodium is to utilize to contain very big natural sodium salt raw material, and for example trona-be a kind of concentrated crystal soda also has the mineral products sodium carbonate decahydrate.These raw materials are to become calcined soda by calcining with subsequently burning excess processing mostly.Jia Gong shortcoming is that the receptivity of calcined soda is not high like this.
Therefore, the objective of the invention is to solve the natural matter from cheap and easy to get, promptly mainly is sodium carbonate decahydrate Na
2CO
310H
2O prepares the existing technical barrier of active sodium carbonate.
The objective of the invention is the respond preparation method of active yellow soda ash of sulfurous gas, and require the gas cleaning degree is higher than 90%, and the utilization ratio of yellow soda ash also is higher than 90%, the feature of present method is to consist of Na with containing
2CO
310H
2O(is 10H wherein
2O represents crystal water) the progressively dehydration in drying process of the starting raw material of solid sodium carbonate decahydrate, obtain crystal water content corresponding to consisting of Na
2CO
3NH
2O(is n=0 to 1 wherein) yellow soda ash, carry out the exsiccant condition and remain below 32 ℃ for the solids temperature, degree of drying reaches its crystal water content corresponding to Na
2CO
3NH
2The composition of O, wherein n=0 to 5.
On behalf of sodium carbonate decahydrate, 32 ℃ temperature limitation be dissolved in melting temperature in itself crystal water.Be more rudimentary hydrate in disclosing and, be lower than under described 32 ℃ of ultimate temperature conditions exactly, gradating herein, and the crystal water component is reduced by this decahydrate as one of fact of foundation of the present invention.By such step, just might obtain about 10 meters squared per gram of specific surface area, the active sodium carbonate of the about 0.4 gram/cubic centimetre of tap density or its monohydrate.The feature of the solid product produced of method is that sulfurous gas is had very strong reactive behavior thus, thereby the transformation efficiency that participates in the material of reaction is more than 90% of its stoichiometric quantity.
Reverse situation, if dewater being higher than fusing point (32 ℃) temperature of this decahydrate in its crystal water, then original crystalline structure is disintegrated fully.The solids that generates with this method is the few agglutinating matter of a kind of hole mutually, and its specific surface area is less than 1 meters squared per gram, in fact to the reactionless activity of sulfurous gas.
Also have further development by initial purpose of the present invention, the required temperature condition that is lower than its fusing point when finding above-mentioned sodium carbonate decahydrate dehydration exactly must remain to its composition is low to moderate at least corresponding to pentahydrate (Na
2CO
35H
2O) till the time, after composition is lower than pentahydrate, promptly can unrestrictedly improves drying temperature, thereby can accelerate drying process speed, when adopting this kind mode, porosity structure is unlikely disintegrates for this.Active sodium carbonate or its monohydrate produced of method possesses aforementioned physical properties and chemically reactive thus.
Therefore, carrying out the exsiccant advantageous manner is that the first step adopts 10-31.9 ℃, and its composition is reached corresponding to pentahydrate Na
2CO
35H
2O, the second step employing is carried out drying for 33-150 ℃ then.
Dry lower limit temperature is 10 ℃, and this is the dynamic conditions according to this drying process, and making it still can be definite finishing dehydration within reasonable time.
The second step exsiccant ceiling temperature is 150 ℃, and this is the effluent gas temperature that produces by common combustion processes and definite.Present method just can use these stack gases.
The mode of carrying out this dry process can be to adopt decompression or vacuum condition, or air-dry in natural climate, or in inert gas flow with fluidized-bed mode drying, the moisture content of this rare gas element should be lower than the 3.2%(volume).In preparation process, the yellow soda ash of this heat can be applied to needn't provide the energy in the flue gas desulfurization (FGD) reaction thereafter more specially.In drying process, can improve the temperature of the thing that is dried.
Above-mentioned active sodium carbonate preparation method also can be applicable to the reactivate of low activity yellow soda ash, and for example the calcined soda with fine powdered mixes with water, and the mixed weight ratio is 1: 1.7 or higher, by the present invention formed mashed paste mixture is carried out drying then.
Below each example more detailed description prepare the method for active sodium carbonate by the present invention, and by the application method and the effect of products made thereby of the present invention.
Example 1
In the laboratory, be that the sodium carbonate decahydrate of 0.25-0.33 millimeter is in 24 ℃ be lower than under the 2 handkerchief reduced pressure dry 1 hour with granularity.With the yellow soda ash semihydrate (Na that obtains thus
2CO
3H
2O) place reactor, contact with the gas mixture of following composition: the sulfurous gas 0.2%(volume), 2%(volume in 150 ℃) water vapor, all the other are nitrogen.Total gas flow rate is 100 ml/min, makes the sulfurous gas sent to reach 1 to the stoichiometric quantity ratio of yellow soda ash, and the average degree of purification of this gas removal sulfurous gas is for being higher than 98%, and the final transformation efficiency of this solids is higher than 99%.
Example 2
Be that the sodium carbonate decahydrate of 0.25-0.33 millimeter is paved into thin layer in 24 ℃ and carried out natural climate air-dry 24 hours with granularity.Carry out chemical analysis after test is finished, it consists of Na
2CO
31.2H
2O.This monohydrate is placed 152 ℃ reactor, contacts with the mixed gas of following composition: the 0.2%(condition) sulfurous gas, 2%(volume) water vapor, all the other are nitrogen.Total gas flow rate is 100 ml/min, and aeration time is after 32 minutes, is 1 corresponding to the sulfurous gas of sending to the stoichiometric quantity ratio of yellow soda ash, and the average degree of purification of this gas removal sulfurous gas is 94%, and the final transformation efficiency of this solids is 96%.
Example 3
With granularity is that the sodium carbonate decahydrate of 0.25-0.33 millimeter dewaters in fluidized-bed, and temperature is 30 ℃, and fluidizing gas is for containing the 2%(volume) water enhanced air.The air line speed of calculating by empty reactor is 0.44 meter per second.After drying operation in 1 hour, generate dihydrate Na
2CO
32H
2O.After operation in 2 hours, finish drying, solid phase is analyzed.The final product of dehydration is monohydrate Na
2CO
3H
2O.This monohydrate is placed 151 ℃ reactor, and contacts: the sulfurous gas 0.077%(volume), 2%(volume with the mixed gas of following composition) water vapor, all the other are nitrogen.Total gas flow rate is 50 ml/min, makes the sulfurous gas sent to reach 1 to the stoichiometric quantity ratio of yellow soda ash, and the average degree of purification of this gas removal sulfurous gas is higher than 92%, and the final transformation efficiency of this solids is 93%.
Example 4
The sodium carbonate decahydrate (weighing 17 grams) of granularity 0.25-0.33 millimeter is dewatered in fluidized-bed in 20 ℃.The original water content of used air is the 0.32%(volume), flow is 0.18 cubic metre/hour.The air line speed of calculating by empty fluidized-bed is 0.44 meter per second.After dry 30 minutes, obtain consisting of Na in fluidized state
2CO
35H
2The product of O.This product used nitrogen gas stream in fixed-bed reactor and be warming up to be no more than 130 ℃ further dry, 15 minutes time of drying.Average temperature rise rate is 7 ℃/minute.The end product of drying is an anhydrous sodium carbonate.In 110 ℃, become the equilibrated water vapor pressure to equal a normal atmosphere with the solid sodium carbonate monohydrate.
Example 5
With granularity is that the sodium carbonate decahydrate (weigh 17 gram) of 0.25-0.33 millimeter dewaters in fluidized-bed in 30 ℃.The original water content of used air is the 2%(volume), flow velocity is 0.26 meter per second.After dry 60 minutes, products therefrom consists of Na in fluidized-bed
2CO
34H
2O.Then the fluidized bed gas temperature is risen to 40 ℃, continued dry 30 minutes, products therefrom is yellow soda ash monohydrate (Na
2CO
31H
2O).
Example 6
Example 4 gained desciccates are placed 150 ℃ reactor, and contact: 870ppm(=0.087%, volume with the mixing of following composition) sulfurous gas, the 2%(volume) water vapor, all the other are nitrogen.Total gas flow rate is 50 ml/min, makes the sulfurous gas sent to reach 1 to the stoichiometric quantity ratio of yellow soda ash, and the average degree of purification of gas removal sulfurous gas is higher than 92%, and the final transformation efficiency of this solids is 94.7%.
In order to prove desulfurization efficiency by the made active sodium carbonate of the present invention, carried out comparative determination, the results are shown in the accompanying drawing.A kind of yellow soda ash reaction bed shown in this figure remove the sulfurous gas effect curve.
W represents the stoichiometric quantity load of machinery systems of this reaction bed, also has the letter justice of dimensionless time, and the stoichiometric quantity ratio of expression NSR(normalization) numerical value reciprocal; E represents its desulfuration efficiency.
A kind of sweetening effectiveness of low reaction activity yellow soda ash is by curve 1 expression.After being prepared into active sodium carbonate by described low reaction activity yellow soda ash, its sweetening effectiveness curve is positioned at curve 2 and 3 scopes that wrapped into.These curves all are to test gained with same reaction conditions: 150 ℃ of temperature; Gas mixture is formed: the sulfurous gas 0.2%(volume), 2%(volume) water vapor, all the other are nitrogen; Granularity is the 0.25-0.33 millimeter.The final transformation efficiency of this low reaction activity yellow soda ash sample is 7.7%, and the transformation efficiency of this high reaction activity solid carbonic acid sodium sample reaches the 90-93% scope.
Claims (5)
1, have preparation method to the yellow soda ash of sulfurous gas reactive behavior, this active sodium carbonate can reach gas purification coefficiency and be higher than 90%, and the yellow soda ash utilization ratio is higher than 90%, it is characterized in that consisting of Na
2CO
310H
2O, wherein 10H
2O represents the solid sodium carbonate decahydrate of crystal water as starting raw material, adopts drying means progressively to dewater, and obtains crystal water content corresponding to consisting of Na
2CO
3NH
2O, the yellow soda ash of n=0 to 1 wherein, wherein this solids is to remain below 32 ℃ of temperature to carry out drying, until its crystal water content corresponding to consisting of Na
2CO
3NH
2O is wherein till the n=0 to 5.
2, by the fs that the process of claim 1 wherein in drying process, the temperature range of this solids is 10-31.9 ℃, and degree of drying reaches it and forms corresponding to its pentahydrate Na
2CO
35H
2O; The temperature range of second drying stage thereafter is 33-150 ℃.
3, by the process of claim 1 wherein that drying process is to carry out in a kind of air-flow, and the moisture content of this air-flow is lower than the 3.2%(volume).
4, by the process of claim 1 wherein that drying process is to carry out in a fluidized-bed.
5, progressively raise by the drying temperature that the process of claim 1 wherein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS984-88 | 1988-02-17 | ||
| CS88984A CS266617B1 (en) | 1988-02-17 | 1988-02-17 | Method of sodium carbonate's higher hydrates drying |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1035272A true CN1035272A (en) | 1989-09-06 |
| CN1016600B CN1016600B (en) | 1992-05-13 |
Family
ID=5343089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88107114 Expired CN1016600B (en) | 1988-02-17 | 1988-10-11 | Method of producting active sodium caurbonate |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPH01252521A (en) |
| CN (1) | CN1016600B (en) |
| CS (1) | CS266617B1 (en) |
| IT (1) | IT1227255B (en) |
| SU (1) | SU1720484A3 (en) |
| YU (1) | YU181788A (en) |
-
1988
- 1988-02-17 CS CS88984A patent/CS266617B1/en unknown
- 1988-09-28 YU YU181788A patent/YU181788A/en unknown
- 1988-09-30 IT IT8822142A patent/IT1227255B/en active
- 1988-10-03 JP JP24755788A patent/JPH01252521A/en active Pending
- 1988-10-11 CN CN 88107114 patent/CN1016600B/en not_active Expired
- 1988-10-14 SU SU884356544A patent/SU1720484A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| SU1720484A3 (en) | 1992-03-15 |
| IT8822142A0 (en) | 1988-09-30 |
| CS266617B1 (en) | 1990-01-12 |
| CN1016600B (en) | 1992-05-13 |
| YU181788A (en) | 1990-02-28 |
| IT1227255B (en) | 1991-03-28 |
| CS98488A1 (en) | 1989-04-14 |
| JPH01252521A (en) | 1989-10-09 |
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