CN1089235A - The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia - Google Patents
The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia Download PDFInfo
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- CN1089235A CN1089235A CN 93115453 CN93115453A CN1089235A CN 1089235 A CN1089235 A CN 1089235A CN 93115453 CN93115453 CN 93115453 CN 93115453 A CN93115453 A CN 93115453A CN 1089235 A CN1089235 A CN 1089235A
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- Prior art keywords
- bicarbonate
- sodium
- ammonia
- exchange
- sodium bicarbonate
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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
- C01D7/02—Preparation by double decomposition
Abstract
The present invention relates to a kind of is raw material with sodium sulfate and bicarbonate of ammonia, produce the method for sodium bicarbonate, being characterized in adopting ion exchange resin is medium, by sodium sulfate is separated exchange, cryoconcentration, crystallizing and drying with bicarbonate of ammonia, reaches the purpose of producing sodium bicarbonate (sodium bicarbonate).It is abundant that this method has prepared using, the quality product height, and technology compactness, advanced advantage can direct step output sodium bicarbonates, and cost is low, and equipment is few, and is pollution-free substantially, good in economic efficiency.
Description
The present invention relates to a kind of is raw material production sodium bicarbonate (NaHCO with sodium sulfate and bicarbonate of ammonia
3) method.
Industrial production sodium bicarbonate (sodium bicarbonate) mainly is yellow soda ash (soda ash) is added water and makes alkaline solution in the choline cylinder after, send in the carbonating tower again, pass to carbonic acid gas and carry out carbonization, the sodium bicarbonate crystallization is separated out, make its chemical equation of finished product and be through separation, drying again:
In the soda ash of soda factory was produced, product in the middle of it " weighed alkali " though contain more sodium bicarbonate, owing to also contain other impurity, thus can not be directly as the product use of sodium bicarbonate, its major ingredient is: NaHCO
368～74%, Na
2CO
35～7%, NH
4HCO
33～4%, NaCl＜0.5%, H
2O 16～21%, can only be that this " heavy alkali " is dissolved in water in the choline cylinder, send in the decomposition tower again and decompose with steam-heated cal(l)andria, to decompose ammonia and carbonic acid gas wherein, solution after the decomposition is alkali aqueous solution after cooling off, again this solution is sent into carbonating tower and carries out carbonization, the sodium bicarbonate crystallization is separated out, through separate, dry and finished product.
Its main chemical reactions formula is:
In oven dry, because processing requirement height, temperature is high slightly, then entropy increases factor and plays a leading role and reversed reaction takes place, cause sodium bicarbonate to be decomposed into yellow soda ash (soda ash) and influenced the quality of sodium bicarbonate (sodium bicarbonate), therefore the production process of sodium bicarbonate is more than soda ash, and its price is higher than the soda ash price.
On the other hand, in the production " heavy alkali " calcining is soda ash, its " caustic soda rate " is about 70%, needs weight in wet base alkali more than one ton, just can be sintered into one ton of soda ash, and the price of soda ash is lower than sodium bicarbonate.Therefore, if can directly make sodium bicarbonate, favorable economic benefit is then arranged.
In replacement(metathesis)reaction and replacement(metathesis)reaction with sodium sulfate replacement sodium-chlor and bicarbonate of ammonia with bicarbonate of ammonia and sodium-chlor, product is a sodium bicarbonate in the middle of it, but still because of containing more impurity, and dry reasons such as wayward, and can not directly use, just its calcining is used for soda ash.
Chinese patent 89102196.5 discloses a kind of " material and bicarbonate of ammonia with contains sodium sulfate are the producing soda by solid-phase process of raw material ", belongs to the metathesis working system.The urao of material of its employing contains sodium sulfate such as natural saltcake, thenardite, mirabilite hydrate, contains sodium sulfate etc. generate sodium bicarbonate with the solid ammonium bicarbonate reaction, make soda ash again.Its process is mainly carried out in the solid phase scope, the material that is about to contains sodium sulfate is mixed with saturated solution by a certain percentage, the solid ammonium bicarbonate that further adds through screening makes it carry out solid state reaction again, generally after the bicarbonate of ammonia particle is converted into sodium bicarbonate more than 90%, thinks that reaction finishes substantially.Utilize products obtained therefrom sodium bicarbonate and ammonium sulfate solubleness different in solution, and, obtain soda ash through washing, dehydration, calcining again its separation.
Because filtrate filtered contains a large amount of by product ammonium sulfate, also mix simultaneously a small amount of unreacted sodium sulfate, bicarbonate of ammonia are arranged, and sodium bicarbonate, therefore need again the further evaporation concentration of filtrate to be obtained the ammonium sulfate finished product to after its further cooling, crystallization, filtration, the separation.
In the specification sheets of this application, make referrals to the weight in wet base alkali after washing, dehydration, with the known oven drying at low temperature technology in present technique field, can be made into heavy alkali (sodium bicarbonate) product.
Above method exists raw material availability not enough, and the purity of product sodium bicarbonate and ammonium sulfate is difficult for improving, and the water for cleaning amount is big repeatedly, and separation circuit is many, the problem that cost is high.As being mingled with impurity between sodium bicarbonate crystal, need to clean, and sodium bicarbonate is subjected to the influence of its solubleness in cleaning, its crystallization is easily dissolved in cleaning and is run off, and the remaining unsaturation that it is difficult for separating out is partly in this solution, participate in the ammoniumsulphate soln with other unreacted reactants, need with its again crystallization separate out.Owing in this reaction soln, exist unreacted intact bicarbonate of ammonia and sodium sulfate, so exist Na in the solution
2SO
4, NH
4HCO
3, NaHCO
3, (NH
4)
2SO
4Quaternary system, and in the water salts solution of this quaternary system, be to be difficult to obtain two kinds of pure products from two kinds of raw materials.
The objective of the invention is to overcome the weak point of existing system sodium bicarbonate technology, propose a kind of new be the method that sodium bicarbonate is produced in the single-phase decomposition of raw material with sodium sulfate and bicarbonate of ammonia, to improve the quality of products, make full use of raw material, simplify technology and reduce cost.
The objective of the invention is to finish by the following technical programs:
A kind of method with sodium sulfate and the single-phase decomposition system sodium bicarbonate of bicarbonate of ammonia, with sodium sulfate and bicarbonate of ammonia is raw material, adopt ion-exchange and osmotic technique to carry out, it is characterized in that described exchange is is medium with the Zeo-karb, the NH in the bicarbonate of ammonia
+ 4With the Na in the sodium sulfate
+Separate exchange, producing product sodium bicarbonate and ammoniumsulphate soln, is medium with the ion-exchange membrane that ion exchange resin was pressed into again, sodium hydrogen carbonate solution is carried out electrodialysis concentrates, the cycle operation of crystallisation by cooling, by separation, crystallization and drying, produce sodium bicarbonate (sodium bicarbonate)
Method of the present invention also has following technical characterictic:
Can separate sodium hydrogen carbonate solution direct heating, concentrated, dry, the calcining that exchange gets with Zeo-karb, produce soda ash (yellow soda ash).
Can separate the ammoniumsulphate soln that gets of exchange with Zeo-karb and heat, concentrate, produce ammonium sulfate product.
The inventive method compared with prior art has the following advantages: 1.. because raw material reaction carries out under controllable condition respectively, avoided other raw material and by product, so products obtained therefrom purity height, quality are good to the mixing of product; 2.. because the quality height of the sodium bicarbonate that produces, can be direct a step produce sodium bicarbonate, do not need substantially to product clean repeatedly, separation, impurity elimination, need weight alkali calcining is become soda ash thereby saved, be the operation of sodium bicarbonate by the soda ash carbonization again, reduced production cost greatly; 3.. since deducted repeatedly clean, links such as separation, impurity elimination, small investment of production equipment is easy to go into operation; 4.. there is not other byproduct emission in the production, basic non-environmental-pollution.
Fig. 1 is a process flow diagram of the present invention;
The below is described in detail technical process of the present invention:
The present invention adopts:
(1). with cationic ion-exchange resin, to Na+And NH+ 4Exchange, thereby reached production sodium acid carbonate (NaHCO3) and ammonium sulfate (NH4）
2SO
4Purpose. This be since in the cationic ion-exchange resin its fixing skeleton be connected with many can movable function base, this function base cation that can dissociate out can carry out the equivalent exchange with the cation of external identical charges symbol on every side.
This exchange capacity according to resin is subjected to resin on very large this character of impact of different ions selectivity factor size, in weak solution and under the normal temperature, cationic valence mumber is higher, it is selectively larger, in same valence mumber, the hydration radius of ion is less, and namely atomic number is larger, and its affinity is also larger. In addition, this different selectivity factor also shows different impacts in the different degrees of cross linking, and namely in rarer solution, the resin cation of the different degrees of cross linking is to NH+ 4The selection coefficient all than Na+Greatly, so NH+ 4Than Na+Be easy to the absorption exchange.
But in the solution of high concentration, (be commonly considered as more than 3 mol/l), because aquation is insufficient, even ion is close to exposed, when the state of ion own is only arranged, when atomic number increased, ionic radius increased, and ion surface charge density reduces relatively, hydration also reduces, sometimes even antipodal exchanging order occurs.
The present invention has utilized this character, in general solution to select the larger NH of coefficient (affinity)+ 4To Na+Exchange, and to selecting the Na of coefficient less+Na that then can high concentration+To NH+ 4React exchange, thereby reach repeatedly the purpose that exchanges, recycles.
As in experimental study, adopt carbonic hydroammonium (NH4HCO
3) be made into wherein NH of 2.2mol(+ 4Be 39.6 grams per liters) in Na base cationic ion-exchange resin, exchange, make resin-bonded NH+ 4, and with Na+Be swapped out and HCO3 -In conjunction with and be sodium acid carbonate (NaHCO3) flow out, again with the sodium sulphate (Na of 1.3mol2SO
4) (Na wherein+Be 59.8 grams per liters) carry out the backwash exchange, make resin again in conjunction with Na+Base, and with NH+ 4Be swapped out and SO4 -In conjunction with and be ammonium sulfate ((NH4）
2SO
4) flow out, so repeatedly resin being exchanged the purpose that reaches output dibastic sodium phosphate and ammonium sulfate with anticommuting with raw material carbonic hydroammonium and sodium sulphate, the chemical equation of its exchange process is (representing resin solid skeleton part with R):
Just exchange:
Anticommuting:
From above chemical equation bicarbonate of ammonia (NH as can be seen
4HCO
3) and sodium sulfate (Na
2SO
4) all be respectively with exchange resin on exchangable ion react and output sodium bicarbonate (NaHCO respectively
3) and ammonium sulfate (NH
4)
2SO
4.
(2). with ion-exchange membrane the sodium hydrogen carbonate solution of output is carried out cryoconcentration, crystallization, drying treatment, with reach receive the purpose of sodium bicarbonate product.
This is owing in last treating processes, through effusive solution is the sodium hydrogen carbonate solution that contains about 9% by the exchange resin exchange with bicarbonate of ammonia, obtain sodium bicarbonate crystal as need, still needs and handles through cryoconcentration.Because sodium bicarbonate crystallization in its solution is relevant with its solubleness and temperature.Therefore, its formation supersaturated solution crystallization is separated out, should not take the spissated way of direct heating for obtaining sodium bicarbonate.
The present invention adopts the electrodialytic method with ion-exchange membrane, to improve sodium hydrogen carbonate solution concentration, be equipped with refrigeration cycle then, make its formation supersaturated solution and the sodium bicarbonate crystallization is separated out, solution after the crystallization has been dilute solution after filtering, can cooperate original solution to change over to again in the electrodialysis unit of ion-exchange membrane again, proceed to concentrate, concentrate back recirculation cooling to reach the purpose that the sodium bicarbonate crystallization is separated out.
Ion-exchange membrane described here is a kind of film that ion exchange resin is pulverized, formed by polymer binder and strongthener compacting, with the Zeo-karb compacting is anode membrane, with the anionite-exchange resin compacting is cavity block, they have the selection perviousness to positively charged ion in the solution and negatively charged ion, promptly under the effect of DC electric field, anode membrane can only see through positively charged ion, cavity block can only see through negatively charged ion, utilize this electrodialytic character principle, sodium bicarbonate aqueous solution is carried out concentration.
Strength of solution after concentrating by above electrodialysis can reach more than 12%, sends to the water cooler crystallisation by cooling.
Cooled sodium bicarbonate crystallization is sent into heating duct, with hot blast and a small amount of CO after separating
2Carry out the dry sodium bicarbonate product that gets.Dilute solution after the filtration is sent into solution that storage tank and new friend bring and is entered the circulation that electrodialyzer participates in next time simultaneously and concentrate.
Also can will exchange the sodium hydrogen carbonate solution direct heating concentrate drying of back effusive about 9% aborning to produce Na
2CO
3(soda ash) product.
(3). to after exchanging the back effusive ammoniumsulphate soln carrying out evaporation concentration, further crystallisation by cooling is the ammonium sulfate finished product through centrifuge dripping again.
Adopt above method aborning, behind adding sodium sulfate and the bicarbonate of ammonia, products therefrom is sodium bicarbonate and ammonium sulfate, does not have other by product, and basic three-waste free discharge is pollution-free.
Embodiments of the invention: with homemade ∮ 60 * 600mm ion exchange column, in adorn 1.1 liters of 732 Zeo-karbs, prepare 1. 2.2mol bicarbonate of ammonia 1000ml respectively, 2. .1.3mol sodium sulfate 1000ml exchanges processing, receive 9% sodium hydrogen carbonate solution 1330ml and 8% ammoniumsulphate soln 1360ml, (with above solution heat respectively, concentrate, drying treatment can make soda ash (Na
2CO
3) 108 grams, ammonium sulfate (NH
4)
2SO
4123 grams).
With homemade small electrical dialyzer, its specification is electrode area 1.82dm, with the negative and positive exchange membrane totally 20 pairs form membrane stacks, the film useful area is 1.4dm, water distribution system adopts the concurrent direction to carry out in the membrane stack.
Method with above example, prepared 9% sodium hydrogen carbonate solution 1000ml carries out earlier going out sodium bicarbonate 24g with 0 ℃ of crystallisation by cooling, solution is filtered, solution is concentrated in electrodialyzer, get 12% strong solution 550ml, this solution is sent into cooling (0 ℃) again get sodium bicarbonate 29g, more than altogether sodium bicarbonate 53g, solution after the filtration is dilute solution, it is the unsaturated solution of sodium bicarbonate, should be again and former aqueous solution, deliver to the further concentration of electrodialyzer again, produce so repeatedly.
Claims (3)
1, the method for the single-phase decomposition system sodium bicarbonate of a kind of sodium sulfate and bicarbonate of ammonia, with sodium sulfate and bicarbonate of ammonia is raw material, adopt ion-exchange and osmotic technique to carry out, it is characterized in that described exchange is is medium with the Zeo-karb, the NH in the bicarbonate of ammonia
+ 4With the Na in the sodium sulfate
+Separate exchange, and produce product sodium bicarbonate and ammoniumsulphate soln, and be medium with the ion-exchange membrane that ion exchange resin was pressed into again, sodium hydrogen carbonate solution is carried out electrodialysis concentrates and the cycle operation of crystallisation by cooling, by separation, crystallization and drying, produce sodium bicarbonate.
2, the method for the single-phase decomposition system sodium bicarbonate of sodium sulfate according to claim 1 and bicarbonate of ammonia, it is characterized in that and to separate sodium hydrogen carbonate solution direct heating, concentrated, dry, the calcination that exchange gets with Zeo-karb, produce soda ash (yellow soda ash).
3, the method for the single-phase decomposition system sodium bicarbonate of sodium sulfate according to claim 1 and bicarbonate of ammonia is characterized in that can separate the ammoniumsulphate soln that gets of exchange with Zeo-karb heats, concentrates, and produces ammonium sulfate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93115453 CN1089235A (en) | 1993-12-29 | 1993-12-29 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93115453 CN1089235A (en) | 1993-12-29 | 1993-12-29 | The method of the single-phase decomposition system sodium bicarbonate of sodium sulfate and bicarbonate of ammonia |
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| CN1089235A true CN1089235A (en) | 1994-07-13 |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000021887A1 (en) * | 1998-10-13 | 2000-04-20 | Airborne Industrial Minerals Inc. | Method of formulating alkali metal salts |
| CN105600805A (en) * | 2016-01-20 | 2016-05-25 | 西北大学 | Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process |
| CN105645514A (en) * | 2016-01-20 | 2016-06-08 | 西北大学 | Method for separating and purifying ammonium sulfate and sodium sulfate mixed solution during flue gas desulfurizer regeneration |
| CN107416868A (en) * | 2017-06-15 | 2017-12-01 | 山东大正节能环保科技有限公司 | A kind of preparation technology of sodium bicarbonate and ammonium sulfate Chemical Mixed Fertilizer |
| CN109437248A (en) * | 2018-11-23 | 2019-03-08 | 四川金象赛瑞化工股份有限公司 | A method of using saltcake and ammonium hydrogen carbonate as raw material producing soda ash and ammonium sulfate |
| CN109650408A (en) * | 2018-12-08 | 2019-04-19 | 李东田 | A kind of drying means of ammonium hydrogen carbonate |
| CN112850747A (en) * | 2021-02-03 | 2021-05-28 | 浙江艺谛环境设备有限公司 | Method and device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate |
-
1993
- 1993-12-29 CN CN 93115453 patent/CN1089235A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000021887A1 (en) * | 1998-10-13 | 2000-04-20 | Airborne Industrial Minerals Inc. | Method of formulating alkali metal salts |
| CN105600805A (en) * | 2016-01-20 | 2016-05-25 | 西北大学 | Method for separating and purifying ammonium sulfate from by-product solution in flue gas desulfurizing agent regeneration process |
| CN105645514A (en) * | 2016-01-20 | 2016-06-08 | 西北大学 | Method for separating and purifying ammonium sulfate and sodium sulfate mixed solution during flue gas desulfurizer regeneration |
| CN105645514B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | The isolation and purification method of ammonium sulfate and sodium sulphate mixed solution in a kind of fume desulfurizing agent regenerative process |
| CN105600805B (en) * | 2016-01-20 | 2017-06-16 | 西北大学 | A kind of method that ammonium sulfate is isolated and purified in the regenerative process by-product solution from fume desulfurizing agent |
| CN107416868A (en) * | 2017-06-15 | 2017-12-01 | 山东大正节能环保科技有限公司 | A kind of preparation technology of sodium bicarbonate and ammonium sulfate Chemical Mixed Fertilizer |
| CN109437248A (en) * | 2018-11-23 | 2019-03-08 | 四川金象赛瑞化工股份有限公司 | A method of using saltcake and ammonium hydrogen carbonate as raw material producing soda ash and ammonium sulfate |
| CN109650408A (en) * | 2018-12-08 | 2019-04-19 | 李东田 | A kind of drying means of ammonium hydrogen carbonate |
| CN112850747A (en) * | 2021-02-03 | 2021-05-28 | 浙江艺谛环境设备有限公司 | Method and device for preparing ammonium sulfate and sodium bicarbonate by using sodium sulfate and ammonium bicarbonate |
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