CN1010305B - Process for preparing organic base from aqueous solution of alkali metal bicarbonate and hydrochloride organic base containing nitrogenous - Google Patents
Process for preparing organic base from aqueous solution of alkali metal bicarbonate and hydrochloride organic base containing nitrogenousInfo
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- CN1010305B CN1010305B CN 85105969 CN85105969A CN1010305B CN 1010305 B CN1010305 B CN 1010305B CN 85105969 CN85105969 CN 85105969 CN 85105969 A CN85105969 A CN 85105969A CN 1010305 B CN1010305 B CN 1010305B
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- hydrochloride
- aqueous solution
- organic base
- amine
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Abstract
The present invention relates to a method for producing water insoluble nitrogenous organic alkali by using alkalic hydrocarbonate and alkalic hydrochloride. According to the method, water solution (11) is treated by complements (12) of the alkalic hydrochloride, and generated liquid (18) is treated by an alkaline agent (30) which can be used for decomposing the hydrochloride. In a method for producing sodium bicarbonate by an amine method, the present invention is used for regenerating amine.
Description
The invention relates to by the aqueous solution of alkali metal hydrocarbonate and the hydrochloride of water-insoluble nitrogenous organic base and produce for example method of amine of water-insoluble nitrogenous organic base.
The method of producing saleratus and sodium bicarbonate is known, according to this method, the aqueous solution of Repone K or sodium-chlor mixes with the organic solution of water-insoluble amine, the mixture that the obtains gas processing that contains carbonic acid gas, carry out gravity separation then, the water suspension of saleratus or sodium bicarbonate is separated from the organic solution of the hydrochloride of amine, handle this suspensoid, from mother liquor, isolate solid carbon potassium hydrogen phthalate or sodium bicarbonate that it contains, (English Patent-A-1 and amine is regenerated from the organic solution of the hydrochloride of amine, 082, triumphant damp aluminium of 436(and the Kaiser AIuminum ﹠amp of pharmaceutical chemicals company; ChemicaI COrporation) page 2 the 105th row is to page 3 the 5th row; Central patent index, basic abstract journal, E fascicle, 49 weeks, 1972, Derwent Publications Ltd., London, digest 38430T-E: the Japanese patent application-A-7241237(Israel mining industry research and development Israel Mining lnd.Inse.Res.﹠amp of institute; Dev.)).
Phrase " amine method " (amines meenod) refers to this currently known methods of producing saleratus or sodium bicarbonate in the following description.
In this known method, the mother liquor that alkali metal hydrocarbonate is saturated also contains the hydrochloride of amine by chance.Particularly the amine when use is to contain the primary alkyl amine that is less than 18 carbon atoms in triethylamine or its molecule, contains the primary alkyl amine (Rohm of about 12 to 14 carbon atoms in for example known commodity its molecule of Primene 81R by name; Haas) like this really the time.In the known amine method of using triethylamine, handle mother liquor is dissolved in amine wherein with decomposition hydrochloride with alkaline agent (calcium hydroxide), and collection amine (Israel patent-A-33, the 551(Israel mining industry research and development IMI of institute (TAMI) Institutefor Research and Development) the 8th page, embodiment 3).This currently known methods of regenerated amine comprises the luxus consumption of alkaline agent, and wherein major part in fact invalidly consumes the sodium bicarbonate in decomposition nut liquid.
The present invention overcomes this shortcoming by a kind of method is provided, other are all identical for this method, only make the insoluble nitrogenous required alkaline agent consumption of organic bases of recycle-water in the hydrochloride that may reduce the water-insoluble nitrogenous organic base from be dissolved in the alkali metal hydrocarbonate aqueous solution.
Therefore, the invention relates to the method for producing water-insoluble nitrogenous organic base by the hydrochloride of the aqueous solution of alkali metal hydrocarbonate and water-insoluble nitrogenous organic bases; According to the present invention, this aqueous solution at first uses the fill-in of the hydrochloride of nitrogenous organic base to handle, and handles with decomposing the alkaline agent that is dissolved in the hydrochloride in this aqueous solution then.
Nitrogenous organic base is any water-insoluble nitrogenous organic reaction agent that enough alkalescence is arranged according to definition in the method according to the invention, and this reagent and hcl reaction are given birth to alkaligenous hydrochloride.Phrase " water-insoluble " (Water-insoluble) is interpreted as that its meaning is that the solubleness of nitrogenous organic base in water is not more than 2% of solution weight, best 1%.
This aqueous solution is saturated by the hydrochloride institute of the nitrogenous organic base that produces usually.Its hydrochloride content depends on various factors, particularly depends on the nitrogenous organic base and the temperature of generation.And it can be by the saturated or unsaturated solution of alkali metal hydrocarbonate.For example, this solution can be to contain 0.05%(weight at least) hydrochloride of organic bases and 1%(weight at least) solution of alkali metal hydrocarbonate, particularly contain 0.1% to 10%(weight) hydrochloride and 1% of the nitrogenous organic base that produces is to 9%(weight) aqueous solution of alkali metal hydrocarbonate.The method according to this invention is suitable for the situation by the simultaneously saturated aqueous solution of the hydrochloride of the nitrogenous organic base that produces and alkali metal hydrocarbonate.The aqueous solution can contain other dissolved substances at the appropriate time, for example basic metal or alkaline earth metal chloride.
The effect of nitrogenous organic base hydrochloride fill-in is to decompose alkali metal hydrocarbonate in this aqueous solution by generating alkali metal chloride and nitrogenous organic base.The quantity of preferably employed hydrochloride fill-in is enough decomposed the whole alkali metal hydrocarbonates in this aqueous solution according to the present invention.The amount of hydrochloride fill-in can be greater than with respect to the amount of decomposing necessary this fill-in of whole alkali metal hydrocarbonates institute in this aqueous solution, with the accelerate decomposition alkali metal hydrocarbonate.
When this aqueous solution uses the fill-in processing of hydrochloride to finish, collect the organic phase that contains nitrogenous organic base, contain the water of dissolved alkali metal chloride and the hydrochloride of dissolved nitrogenous organic base.
Before water is handled with alkaline agent, the separated from one another and recovery organic phase with this two-phase.This separates available known appropriate method and carries out; Usually use gravity separation, it can carry out under gravity or with centrifuging.
Alkaline agent can be can decompose hydrochloride and produce nitrogenous organic base and with any alkali of immiscible all the other compounds of nitrogenous organic base.Alkaline agent is preferably selected from inorganic strong alkali, and particularly pH value equals 11 at least more preferably greater than 12 mineral alkali.The example that is suitable for as the mineral alkali of alkaline agent is carbon metal and alkaline earth metal carbonate, oxide compound and oxyhydroxide; Preferably use water miscible mineral alkali, particularly sodium oxide and sodium hydroxide.At alkaline agent is under the situation of water miscible mineral alkali, and the latter can use with the form of the aqueous solution easily.
Contain two immiscible phases at the reaction mixture of handling the back collection with alkaline agent, one of them contains the nitrogenous organic base of generation.In order to collect the latter, make reaction mixture carry out gravity separation fully; The solvent that adds nitrogenous organic base in advance is favourable.The character of institute's solvent-applied and the selection of quantity are by the needs decision, i.e. the viscosity of the solution of solvent and nitrogenous organic base formation does not influence gravity separation fully.So the viscosity that the organic solvent of selection is preferably under the service temperature is not more than 3 centipoises, preferably 1 centipoise.In addition, safe and easy to use owing to considering, select flash-point to be higher than the organic solvent of the low volatility of service temperature.The selection of organic solvent also can be by the purpose decision of nitrogenous organic base, for example its objective is that with previously described amine method be when producing sodium bicarbonate and producing the organic solution of amine, preferably select such organic solvent, except above-mentioned character, its characteristics are under moderate temperature, be usually less than 100 ℃, particularly 15 ℃ to 70 ℃, can high-speed absorbing carbon dioxide.
The organic solvent of using preferably makes the proportion of the proportion of the organic solution that contains nitrogenous organic base less than water.To such an extent as to solvent so expediently selection water proportion and the difference between the organic solution proportion minimum be 5% of above-mentioned organic solution proportion, more preferably greater than 30% of this proportion.
Because consider economy, the method according to this invention is preferably carried out at low temperatures, generally be lower than under 60 ℃ the temperature preferably 15 to 40 ℃.In this case, organic solvent can be selected from hydro carbons expediently, contains 25% to 75%(weight to such an extent as to its amount is regulated organic solution like this) nitrogenous organic base.Applicable within the scope of the invention representative examples of organic is dimethylbenzene, butylbenzene, ethyl methyl benzene, particularly known petroleum solvent and commodity solvent, the mixture of commodity Isoper(isoparaffin by name) (ESSO Oil Esso), the mixture of Solve-sso(aromatic substance) (ESSO Oil), the mixture of Shellsol AB(aromatic substance) (Shell of the Shell Oil Co.) Shellsolk(mixture or fatty compounds).
Before handling, in processing or after handling, all can use solvent with alkaline agent.
The method according to this invention generally is applicable to any water-insoluble nitrogenous organic base as defined above, and it can generate water miscible organic hydrochloride by enough hydrogenchloride; The solubleness that this method is specially adapted to produce in water is not more than 0.5%(weight) nitrogenous organic base, and the solubleness that is best suited in water is lower than 0.05%(weight) the production of nitrogenous organic base.For example present method is applicable to and produces imines and its derivative, quaternary amine, amine and its derivative.The method according to this invention similarly is applicable to produces primary amine, secondary amine or tertiary amine.Found that present method is used for producing primary amine from the hydrochloride of primary amine especially easily, particularly contained 7 to 18(particularly 12 to 14) the primary alkyl amine of carbon atom, found that present method is used for producing sodium bicarbonate by previously described amine method expediently.So the method according to this invention can combine with above-mentioned amine method expediently, organic amine solution then is applied to regenerate.
Therefore, the present invention also is about producing the method for sodium bicarbonate, generate the mixture of sodium chloride aqueous solution and water-insoluble amine organic solution according to present method, the mixture that the produces gas processing that contains carbonic acid gas, the organic solution of the water suspension of generation sodium bicarbonate and the hydrochloride of amine is handled the water suspension of sodium bicarbonate and is isolated solid sodium bicarbonate and the mother liquor that wherein contains; According to the present invention, this mother liquor is handled with the organic solution of the hydrochloride of at least a portion amine, being recycled in the said mixture organic amine solution and the aqueous solution collects respectively, the aqueous solution is handled with the alkaline agent of the hydrochloride that can decompose the amine that wherein contains, and the amine and the water that are recycled in the said mixture of generation are collected with gravity separation.
In the method according to the invention, the quantity of the organic solution of the hydrochloride of application amine preferably enough makes all carbonate ammonia natriums decomposition in the mother liquor.
In the optimum implementation of sodium bicarbonate method produced according to the invention, the alkaline agent of application is the aqueous solution of sodium hydroxide, and from all the other waters that gravity separation goes out adding sodium-chlor is wherein arranged, and is recycled in the original mixture then.Go out remaining aqueous phase for sodium-chlor is added to from gravity separation, for example may make remaining water penetrate the accumulation horizon of rock salt.
Show in the explanation of feature of the present invention and the details sketch from following accompanying drawing, accompanying drawing represents to produce with previously described amine method the simple synoptic diagram of sodium bicarbonate device, and this synoptic diagram comprises optimum implementation of the present invention.
Device shown in the figure comprises crystallisation chamber 1, to wherein adding saturated basically sodium chloride aqueous solution 2 continuously, is insoluble to the primary amine organic solution 3 of sodium chloride aqueous solution and contains the gas 4 of carbonic acid gas.The organic solution of primary amine for example can be concentration 50%(weight) Primene81R amine (Lu Mu and the ROhm of Haars Co., Ltd; Haas) xylene solution, Prmene81R are the primary alkyl amine that contains 12 to 14 carbon atoms in its molecule.Gas 4 preferably contains 60% to 80%(weight) rich gas of carbonic acid gas, residual gas that carbonic acid gas for example is sintered into yellow soda ash (Sodium monoeurbonate) generation by lime-kiln gas and sodium bicarbonate mixes generation in the proper ratio.The gas volume of using should enough change into sodium bicarbonate with the most of sodium-chlor in the solution 2.As alternative method, for example the partially carbonized of mixture that carry out of lime-kiln gas can be before the processing in the crystallisation chamber 1 with the gas that contains low levels=carbonoxide.
Expel liquid 5 from crystallisation chamber 1, and liquid 5 is made up of the mixture of the aqueous solution and organic solution, and contains sodium bicarbonate crystal in suspensoid.This liquid 5 is transported to gravity separator 6, and the organic solution 7 usefulness gravity of the hydrochloride of amine are separated from the aqueous slurry 8 of sodium bicarbonate crystal there.The latter guides to coarse filtration equipment or filter plant 9, collects solid sodium bicarbonate 10 and mother liquor 11 there respectively.Mother liquor is saturated and contain the hydrochloride of dissolved amine by sodium bicarbonate.
Organic solution 7 separated into two parts 12 and 13 of the hydrochloride of amine according to the present invention, a part 12 and mother liquor 11 import reaction chamber 14, carry out powerful the stirring therein with the reaction between the hydrochloride that impels sodium bicarbonate and amine, the result generates the sodium-chlor that is dissolved in the aqueous solution, be dissolved in the primary amine in the organic solution, and carbonic acid gas.Whole sodium bicarbonate in the enough decomposition nut liquids of the amount of part 12.For the reaction between the hydrochloride that promotes sodium bicarbonate and amine, with reaction chamber 14 heating, fall as be heated to 60 ℃, and the carbonic acid gas that wherein generates is extracted out with vacuum pump 15.Send crystallisation chamber 1 expediently back to by the carbonic acid gas 28 that pump 15 is extracted out from reaction chamber 14.
By the liquid 16 that the organic solution of sodium chloride aqueous solution that dilutes and amine is formed, discharge from reaction chamber 14; This liquid 16 is guided to gravity separator 17, from then on collects the sodium chloride aqueous solution 18 of dilution and the organic solution 19 of amine respectively.
The aqueous solution 18 of the sodium-chlor of dilution also contains the hydrochloride of dissolved amine.This solution is transported to reaction chamber 29, and to the aqueous solution 30 of hydro-oxidation sodium wherein, its quantity is enough decomposed the hydrochloride of all amine that exist in sodium chloride solution 18.This aqueous solution 30 can be by containing 30% to 60%(weight) aqueous solution of sodium hydroxide forms, and this aqueous solution is by being equipped with mercury or the optionally aqueous solution production of electrolytic sodium chloride in the electrolyzer of permeable membrane.The aqueous solution alternatively, it also can be to contain 10% to 20%(weight) sodium hydroxide and 10% is to 20%(weight) aqueous solution of sodium-chlor, this aqueous solution is by electrolytic sodium chloride aqueous solution production in diaphragm cell.
Guide to gravity separator 32 from the liquid 31 that reaction chamber 29 is discharged, collect the sodium chloride aqueous solution 33 of dilution of the hydrochloride that does not contain amine and the organic solution 34 of amine thus respectively.
Then the sodium chloride aqueous solution 33 of dilution is introduced in the rock salt accumulation horizon 20, the saturated aqueous solution 21 of the sodium-chlor of a great deal of is drawn out of thus, and merges with initial sodium-chlor stream 2.
The organic solution 19 and 34 of the amine of collecting from gravity separator 17 and 32 all with organic solution 3 merging of initial amine, and introduce in the crystallisation chamber 1 with the latter.
As alternative method, all or part of 22 in the organic solution 19 and 34 of amine merges with the organic solution 13 of the hydrochloride of part amine.
According to the improvement project of present method, the organic solvent 35 of amine is introduced reaction chamber 29, so that promote the gravity separation in the gravity separator 32.As alternative method, organic solvent 35 can mix with the aqueous solution 18 or liquid 31.
The organic solution 13(of the hydrochloride of part amine arbitrarily mixes with the organic solution 22 of amine then) be used in the technology of amine known method and handle with regenerated amine.For this reason, this organic solution 13 is delivered to reaction chamber 23, water suspension 24 with itself and calcium hydroxide stirs there, and the reaction mixture 25 of generation is delivered to gravity separator 26, collects the aqueous solution 27 of calcium chloride from this separate chamber respectively and is recycled to the organic solution 3 of the amine of crystallisation chamber 1.
The following examples are used to illustrate the present invention.
The use per kilogram contains the sodium chloride aqueous solution of 100g sodium-chlor, this solution hydrochloride " Primenc 81R " (Lu Mu and ROhm of Haars Co., Ltd of amine; Haas) saturated.Like this, this solution of per kilogram contains the 2.8g carbon that the hydrochloride by amine provides.
52.7g the above-mentioned aqueous solution and 1.82cm
3The normal solution of sodium hydroxide mixes, and then 5g organic solvent " Shellsolk " (Shell Oil Co.) is added wherein.
After stirring evenly, the mixture of generation is used gravity separation 24 hours, collects water, and its remaining amine content is measured by measuring carbon: the concentration 0.033g that tries to achieve per kilogram water carbon.
As seen the loss at aqueous phase amine is insignificant.
Claims (9)
1, the method for producing water-insoluble nitrogenous organic base by the hydrochloride of the aqueous solution of alkali metal hydrocarbonate and water-insoluble nitrogenous organic base, described method is that this aqueous solution is handled with the alkaline agent that can decompose this hydrochloride, it is characterized in that before this aqueous solution is handled with alkaline agent, handle with the fill-in of the hydrochloride of this nitrogenous organic base.
2,, it is characterized in that using the fill-in of this nitrogenous organic base hydrochloride of q.s to decompose whole alkali metal hydrocarbonates in this aqueous solution according to the method for claim 1.
3, according to the method for claim 1 or 2, it is characterized in that this aqueous solution is handled with the fill-in of hydrochloride after, the liquid of generation separates by proportion, separate hydrate mutually and organism mutually, this hydrate is mutually with this alkaline agent processing.
4,, it is characterized in that the reaction mixture of generation separates by proportion after this aqueous solution is handled with this alkaline agent according to the method for claim 1 or 2.
5,, it is characterized in that a kind of solvent of this nitrogenous organic base is added in the reaction mixture according to the method for claim 4.
6,, it is characterized in that this alkaline agent is to be selected from water miscible mineral alkali according to the method for claim 1 or 2.
7,, it is characterized in that this alkaline agent that uses is alkali-metal oxyhydroxide according to the method for claim 6.
8,, it is characterized in that this method is to be used for producing the primary alkyl amine that its molecule contains 12 to 14 carbon atoms according to the method for claim 1 or 2.
9, according to the method for claim 1 or 2, the mother liquor that contains suspension in the water that water mixed liquid is a kind of sodium bicarbonate that it is characterized in that this alkali metal hydrocarbonate and water-insoluble nitrogenous organic base hydrochloride, this sodium bicarbonate are to be got by the mixture of the organic solution of carbonated gas processing sodium chloride aqueous solution and a kind of water-insoluble amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105969 CN1010305B (en) | 1984-07-17 | 1985-08-06 | Process for preparing organic base from aqueous solution of alkali metal bicarbonate and hydrochloride organic base containing nitrogenous |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8411424A FR2567878B1 (en) | 1984-07-17 | 1984-07-17 | PROCESS FOR OBTAINING AN ORGANIC NITROGEN BASE INSOLUBLE IN WATER, FROM AN AQUEOUS SOLUTION OF ALKALI METAL BICARBONATE AND CHLORHYDRATE OF SAID BASE, AND PROCESS FOR THE MANUFACTURE OF SODIUM BICARBONATE |
| CN 85105969 CN1010305B (en) | 1984-07-17 | 1985-08-06 | Process for preparing organic base from aqueous solution of alkali metal bicarbonate and hydrochloride organic base containing nitrogenous |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105969A CN85105969A (en) | 1987-02-25 |
| CN1010305B true CN1010305B (en) | 1990-11-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105969 Expired CN1010305B (en) | 1984-07-17 | 1985-08-06 | Process for preparing organic base from aqueous solution of alkali metal bicarbonate and hydrochloride organic base containing nitrogenous |
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| CN106115744B (en) * | 2016-06-22 | 2017-12-01 | 湖南工业大学 | A kind of ultra-fine NaHCO3Particle and its preparation method and application |
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1985
- 1985-08-06 CN CN 85105969 patent/CN1010305B/en not_active Expired
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| CN85105969A (en) | 1987-02-25 |
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