CN1008365B - Process for regenerating an organic solution of a water-insoluble nitrogenous organic base - Google Patents
Process for regenerating an organic solution of a water-insoluble nitrogenous organic baseInfo
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- CN1008365B CN1008365B CN 85104852 CN85104852A CN1008365B CN 1008365 B CN1008365 B CN 1008365B CN 85104852 CN85104852 CN 85104852 CN 85104852 A CN85104852 A CN 85104852A CN 1008365 B CN1008365 B CN 1008365B
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- water
- amine
- hydrochloride
- earth metal
- organic solution
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Abstract
The present invention relates to a method for regenerating an organic solution of water-insoluble organic alkali by an organic solution of alkaline hydrochloride. The solution of alkali hydrochloride is treated by the carbonate of alkali earth metal with the method under the condition of the existence of water, and then the regenerated organic solution of organic alkali containing nitrogen and residual liquid are separated from prepared liquor reaction mixtures. The process is suitable for regenerating amine in the process of preparing alkali metal hydrocarbonate with an amine method.
Description
The present invention relates to by water-fast nitrogenous organic base, example is an amine, the organic solution of hydrochloride reclaim the method for the organic solution of water-fast nitrogenous organic base.
Known a kind of method of making sodium bicarbonate, root accordingly, earlier the aqueous solution of sodium-chlor is mixed with the organic solution of water-fast amine, and then resulting mixture with the gas processing that contains carbonic acid gas, last organic solution (No. the 1082436th, English Patent (Kaiser aluminium and chemical company), page 2 the 105th to 125 row that carries out decant with the hydrochloride of the aqeous suspension (it is collected) of isolating sodium bicarbonate and this amine again; Central Patents Index, Basic Abstracts Journal, Section E, Week, T.49, Derwent Publication Ltd, London, abstract 78430 T-E:Patent Application JP-A-72/41,237(Israel Mining Inds, Inst.Res.﹠amp; Dev.)).
In the narration below, " amine method " just is meant the technology of the known manufacturing alkali metal hydrocarbonate of this kind.
Know that also a kind of decomposing ammonium chloride makes the method for ammonia, root accordingly, earlier aqueous ammonium chloride solution is mixed with the organic solution of water-fast amine, and then a kind of rare gas element or carbonic acid gas cycled through resulting mixture, the ammonia that is produced to remove (Central Patent Index, Basic Abstracts Journal, Section E, Week E/14, Derwent Publications LTd., London(Great Britain), abstract 26992E/14; Patent Application JP-A-57/034,020(TOYO Soda MFG K.K)).
In above-mentioned several currently known methodss,, be ideal and this kind by product is processed with regenerated amine with the organic solution that the form of by product is collected a kind of hydrochloride of amine.Therefore, general normal a kind of method of utilizing, root accordingly, earlier the organic solution of the hydrochloride of amine is mixed with the calcium of suspension or the oxide compound or the hydroxide aqueous solution of magnesium, and then the organic solution and the magnesium chloride of separating or the aqueous solution (English Patent the 1st of calcium chloride of collecting regenerated amine respectively, 082, No. 436 (Kaiser aluminium and chemical company) page 3 the 5th to 9 row; Getral Patents Index, Basic Abstracts Journal, Section E, Week T.49, Derwent Publication Ltd., London, abstract 78430T-E:Patent Application JP-A-72/41,237(Istael Mining Inds.Inst.Res ， ﹠amp; Dev.)).
In this kind currently known methods, use the oxide compound or the oxyhydroxide of calcium or magnesium to come regenerated amine, in advance the operation of calcination of calcium carbonate or magnesiumcarbonate; The shortcoming of this kind operation is to need expensive calcining furnace and relate to expensive energy consumption.
The objective of the invention is to overcome this kind shortcoming, method provides a kind of novelty and method economy of organic solution of the hydrochloride regeneration nitrogenous organic base by nitrogenous organic bases, particularly by the method for the hydrochloride regenerated amine of amine, this method no longer needs expensively calcination of calcium carbonate or magnesiumcarbonate.
Therefore, the present invention relates to by the regenerate method of organic solution of water-fast nitrogenous organic base of the organic solution of the hydrochloride of water-fast nitrogenous organic base, root accordingly, under the condition that has water to exist, the organic solution of the hydrochloride of this alkali is handled with alkaline earth metal compound, this hydrochloride is decomposed and form alkaline earth metal chloride; According to the present invention, having the alkaline earth metal compound of a part at least is to be selected from carbonate.
In the method for the invention, according to definition, nitrogenous organic base is to have enough water-fast nitrogenous organic reactants of alkalescence that can generate the hydrochloride of this alkali with hcl reaction.
In the method for the invention, must select the solvent of the organic solution of nitrogenous organic base, it must the water insoluble and aqueous solution, but it can dissolve the hydrochloride of this alkali again.
The effect of alkaline earth metal compound is to decompose the hydrochloride of this alkali and discharge alkali simultaneously.According to the present invention, having this compound of a part at least is alkaline earth metal carbonate.
The alkaline earth metal carbonate of Shi Yonging can be prepared by any metal of the II a family in the periodic table of elements in the method for the invention.Best lime carbonate, magnesiumcarbonate or the mixture of lime carbonate and magnesiumcarbonate, for example rhombspar of being to use.The ground Wingdale is then especially suitable.
It is desirable to use the alkaline earth metal carbonate of ground form.But its granular size is also unrestricted.In fact, average particulate diameter is advisable to be not more than 25 millimeters, and preferably greater than 10 millimeters, and it is especially favourable to select diameter to be no more than 1 millimeter powder.
Alkaline earth metal compound by at least a portion is to be selected from carbonate, method of the present invention, the operation that can save these carbonate of calcining.Every other factor also is the same, and the relative content of alkaline earth metal carbonate is high more, then saves also correspondingly many more.In fact, be preferably in alkaline earth metal compound, at least 50%(weight should be arranged) be alkaline earth metal carbonate, and preferably surpass 75%(weight); Rest part then can be made up of the oxide compound or the hydroxides of alkaline-earth metal.
According to a particular embodiment of the invention, used whole alkaline earth metal compounds preferably all are with the form of carbonate.Therefore, the attendant advantages of this specific embodiment of the present invention is the device that might not need to calcine alkaline earth metal carbonate fully.In this embodiment of the present invention, if suitable, the amount of alkaline earth metal carbonate can surpass the stoichiometric quantity of amount of the hydrochloride of the alkali be equivalent to be reproduced.
Implement the selection of the optimum temps of this method, depend on various parameter.Particularly depend on nitrogenous organic base, selected alkaline earth metal carbonate and granular size.In general, be preferably and be higher than 50 ℃, and suitable be the temperature that should not be higher than the danger that makes the unsettled temperature of nitrogenous organic base or be decomposed.The temperature of recommending is 50 to 230 ℃, is under a kind of situation of amine at nitrogenous organic base especially; Those at 70 to 200 ℃ and especially 80 to 180 ℃ temperature be preferred temperature, particularly under the situation of primary alkyl amine.
In the method for the invention, should use the water of the quantity of the alkaline earth metal chloride that is enough to dissolve whole formation.But we find preferably to use excessive water, make formed aqueous solution per kilogram contain 4 molar alkaline earth metal chlorides at most; And concentration be lower than 2 the gram branch/kilograms be preferred.
After the organic solution of the hydrochloride of handling amine with alkaline earth metal compound, collect immiscible organic phase and water, this organic phase contains the regenerated organic bases, and this water then contains alkaline earth metal chloride.Can separate two-phase with any suitable currently known methods, for example density separation or centrifugal separation.Can be applied in the method for being narrated in the french patent application No. 53/07226 (solvay company).
Method of the present invention is applicable to nitrogenous organic base usually, this kind nitrogenous organic base is water insoluble and can be fixed as hydrogenchloride the hydrochloride of this alkali, the derivative of for example water-fast imines and their derivative, water-fast quaternary ammonium salt, water-fast amine and amine.But be applicable to primary amine, secondary amine or tertiary amine method indistinction of the present invention, and advantageously be applicable to the primary alkyl amine that contains in the molecule above 7 carbon atoms, for example contain the primary alkyl amine of 10 to 30 carbon atoms, for example Rohm ﹠amp; The commodity Primene JMT of Haas company and Primene 81R, wherein containing 18 and 4 carbon atoms in the molecule of Primene JMT then has 12 14 carbon atoms in the molecule of Primene 81R.
Method of the present invention is specially adapted in above-mentioned usefulness " amine method " preparation sodium bicarbonate, by the organic solution of the hydrochloride regenerated amine of amine.
Therefore, the invention still further relates to a kind of method for preparing alkali metal hydrocarbonate, root accordingly, under the condition that has water to exist, organic solution with gas that contains carbonic acid gas and water-fast nitrogenous organic base is handled alkali metal chloride, collect the organic solution of the hydrochloride of the aqeous suspension of alkali metal hydrogen carbonate sodium and nitrogenous organic bases, handle this aqeous suspension then, therefrom extract the alkali metal hydrocarbonate that is contained, use method of the present invention, the organic solution of regeneration nitrogenous organic base from the organic solution of this hydrochloride.
In the method for manufacturing alkali metal hydrocarbonate of the present invention, advantageously used water-fast primary amine, particularly primary alkyl amine is used as nitrogenous organic base.Preferred primary alkyl amine is that those contain the amine that is no more than 7 carbon atoms in its molecule.
In the advantageous embodiments of a preparation alkali metal hydrocarbonate of the present invention, the alkaline earth metal carbonate carbonic acid gas that is produced and gas that this contains carbonic acid gas in the process that the organic solution of the hydrochloride of nitrogenous organic base is reacted are recycled.
The method of manufacturing alkali metal hydrocarbonate of the present invention advantageously is applied to produce sodium bicarbonate by sodium-chlor.
Therefore, the invention still further relates to and to calcine resultant yellow soda ash by the sodium bicarbonate of method production of the present invention.
Will understand that details of the present invention and characteristics from the explanation of hereinafter accompanying drawing being done.The general arrangement of the factory of sodium bicarbonate is produced in the open-birth with the specific embodiment of the method for production sodium bicarbonate of the present invention of this accompanying drawing.
There is crystallisation chamber 1 in factory shown in the figure, constantly add therein the sodium chloride aqueous solution be actually saturated or sodium oxide aqueous slurry 2, be insoluble to the primary amine organic solution 3 of sodium chloride aqueous solution and contain the gas 4 of carbonic acid gas.The organic solution of primary amine can be a kind of 50%(of containing weight) the dimethylbenzene of primary alkyl amine, Rohm ﹠amp for example; The commodity Primene JMT that Haas company makes, its molecule contains 18 to 24 carbon atoms.Preferably a kind of carbon dioxide enriched gas of gas 4 wherein contains 60%(weight at least) carbonic acid gas.
In crystallisation chamber 1, sodium bicarbonate carries out crystallization, and amine then is converted into the hydrochloride of amine.
Form by the mixture of the organic solution of the hydrochloride of sodium bicarbonate crystallization, crystalline mother solution and amine from the liquid 5 that crystallisation chamber 1 is extracted out.This kind liquid 5 is fed settlers 6, in settler 6, because the proportion difference, and the organic solution 7 of the hydrochloride of amine is separated with aqueous slurry 8.Aqueous slurry 8 is fed dehydration or filtration unit 9, collect solid sodium bicarbonate 10 and mother liquor 11 respectively.After in mother liquor, adding sodium-chlor, it is circulated to crystallisation chamber 1.The solid sodium bicarbonate of collecting 10 can be sent into the calcining furnace (not shown) to produce yellow soda ash.
The method according to this invention is handled the organic solution 7 of the hydrochloride of this amine, with the organic solution of regenerated amine.For this reason, elder generation feeds reaction chambers 16 with the organic solution 7 of the hydrochloride of amine, feeds water 13 and ground Wingdale 14 simultaneously again.Temperature in this chamber 16 is remained on about 130 ℃, and wherein water, Wingdale and organic solution are stirred.The hydrochloride of amine is and calcium carbonate reaction the amine of regenerating (amine that will bear again feeds organic solution) and formation carbonic acid gas and calcium chloride (calcium chloride then feeds the aqueous solution).Chamber 16 is remained on pressurized state seethes with excitement to stop this indoor organic solution and the aqueous solution.
The one side of releasing from reaction chamber 16 is the carbonic acid gas 17 that forms, and this carbonic acid gas circulates with air-flow again, is liquid form mixt 18 on the other hand, wherein contains the organic solution of regenerated amine and the aqueous solution of calcium chloride.This mixture 18 is fed settler 19, therein the organic phase of mixture is separated with water-soluble liquid phase.Use this method, collected one side is the organic solution 3 of amine, and this organic solution is recycled to crystallisation chamber 1, and what collect on the other hand is the remaining aqueous solution 20 that contains lysed calcium chloride.
In the above-mentioned method of being narrated with reference to the accompanying drawings, can regulate the amount of used Wingdale 14, the amount of measuring suitable alkali acid calcium therewith is slightly more than decompose whole stoichiometric quantitys that feed the needed lime carbonate of hydrochloride of the amine in the chambers 16 via organic solution 7.Must there be the water 13 of q.s to dissolve the calcium chloride that all form in chamber 16.Preferably regulate the quantity of used water 13, be less than 2 molar calcium chloride so that contain in the per kilogram residual liquid 20.
In reaction chamber 16, the regeneration of amine may be also not exclusively; Therefore, contain in factory the hydrochloride of the amine of round-robin remnants back and forth in the organic solution 3 of amine.
The application of the method according to this invention, the application of following embodiment relate to the test by the organic solution of the hydrochloride regenerated amine of amine.In these trials, under different operational conditions, handle with the aqeous suspension of lime carbonate water-fast amine hydrochloride organic solution and measure efficient by the hydrochloride regenerated amine of amine.
Used amine is primary alkyl amine Primene JMT(Rohm ﹠amp; Haas company makes), in its molecule, contain 18 to 24 carbon atoms.Use is called Shellsol K(Shell company product) aliphatic organic solvent as the solvent of this organic solution.The water-cooled coalescence that contains carbonic acid gas is recycled.
In the following embodiments, regeneration rate is the amount of the formed amine of hydrochloride of the amine of a unit in the organic solution of beginning.
Embodiment 1
Use the organic solution that a kind of per kilogram contains the hydrochloride of 0.064 molar amine and 1.272 molar amine.The average particulate diameters that this kind organic solutions of 700 grams and the water and 50 of 350 grams are restrained less than 0.1 millimeter and contain 96.5%(weight) the Wingdale of lime carbonate mix.
This mixture was stirred 155 minutes, and temperature remains on 118 ℃, and absolute pressure is 1.5 crust.
After processing, collect the organic phase of 671.6 grams, per kilogram contains the hydrochloride of 1.226 molar amine and 0.160 molar amine.Therefore, the efficient of hydrochloride regenerated amine by the amine in the organic solution of beginning is the 87.5%(mol).
Embodiment 2
Use the organic solution that a kind of per kilogram contains the hydrochloride of 0.068 molar amine and 1.265 molar amine.The average particulate diameters that this kind organic solutions of 1050 grams and the water and 75 of 600 grams are restrained less than 0.1 millimeter and contain 96.5%(weight) the Wingdale of lime carbonate mix.
This mixture was mixed 60 minutes, and temperature remains on about 132.5 ℃, and absolute pressure is 2.8 crust.
After processing, collect the organic phase of 1,004.4 gram, per kilogram contains the hydrochloride of 1.318 molar amine and 0.092 molar amine.Therefore, regeneration efficiency equals the 94.5%(mol).
Embodiment 3
Continue the test of embodiment 2, mixing time is 90 minutes.After the test, collect 1,002.6 gram organic phase, per kilogram contains the hydrochloride of 1.365 molar amine and 0.044 molar amine.Therefore, regeneration efficiency equals the 98%(mol).
Claims (7)
1, by the hydrochloride organic solution of water-fast nitrogenous organic base, the regenerate method of organic solution of water-fast nitrogenous organic base, wherein number of applications is enough to dissolve the water of whole alkaline earth metal chlorides, use alkaline earth metal carbonate, be under 50 to 230 ℃ the condition in temperature, handle the organic solution of the hydrochloride of this alkali, this hydrochloride is decomposed and the formation alkaline earth metal chloride, it is characterized in that having the alkaline earth metal compound of a part at least is to be selected from carbonate.
2,, it is characterized in that used alkaline earth metal carbonate is ground Wingdale according to the method for claim 1.
3, according to the method for claim 1, the amount that it is characterized in that applied water is enough to form per kilogram and contains the aqueous solution that mostly is 4 molar alkaline earth metal chlorides most.
4,, it is characterized in that used whole alkaline earth metal compounds all are with the form of carbonate according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that at nitrogenous organic base be under the situation of amine, be under 70 to 200 ℃ condition, to carry out with alkaline earth metal carbonate to the processing of the organic solution of the hydrochloride of this amine.
6,, after using alkali metal chloride+water and the described water-fast nitrogenous organic base of carbonated gas processing, the organic solution that it is characterized in that the hydrochloride of this water-fast nitrogenous organic base produces according to the method for claim 1.
7,, it is characterized in that this nitrogenous organic base is to be selected from water-fast primary alkyl amine according to the method for claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104852 CN1008365B (en) | 1984-07-17 | 1985-06-20 | Process for regenerating an organic solution of a water-insoluble nitrogenous organic base |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8411425A FR2567879B1 (en) | 1984-07-17 | 1984-07-17 | PROCESS FOR OBTAINING AN ORGANIC NITROGEN BASE INSOLUBLE IN WATER FROM A HYDROSOLUBLE HYDROSOLUBLE OF SAID BASE AND PROCESS FOR THE MANUFACTURE OF SODIUM BICARBONATE |
| CN 85104852 CN1008365B (en) | 1984-07-17 | 1985-06-20 | Process for regenerating an organic solution of a water-insoluble nitrogenous organic base |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104852A CN85104852A (en) | 1986-12-17 |
| CN1008365B true CN1008365B (en) | 1990-06-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104852 Expired CN1008365B (en) | 1984-07-17 | 1985-06-20 | Process for regenerating an organic solution of a water-insoluble nitrogenous organic base |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008365B (en) |
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1985
- 1985-06-20 CN CN 85104852 patent/CN1008365B/en not_active Expired
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| Publication number | Publication date |
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| CN85104852A (en) | 1986-12-17 |
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