CN102320622B

CN102320622B - Ammonium salt recovery method

Info

Publication number: CN102320622B
Application number: CN 201110176246
Authority: CN
Inventors: 季根忠; 朱红旗; 周海滨; 王林超
Original assignee: University of Shaoxing
Current assignee: University of Shaoxing
Priority date: 2011-06-28
Filing date: 2011-06-28
Publication date: 2013-07-31
Anticipated expiration: 2031-06-28
Also published as: CN102320622A

Abstract

The invention discloses an ammonium salt recovery method which is characterized in that aromatic amine is added to a NH4X solid or a NH4X solution for reaction, free ammonia or ammonia water is steamed out under heating conditions, and ammonium salt is obtained. The prepared ammonium salt product has high purity, can be used for further diazotization reaction, and has good industrial application prospects in the selective acylation, alkylation and other reactions of the ammonium salt. Meanwhile, the invention further provides a method which can effectively reduce NH4X solid wastes or waste water and reduce an ammonia nitrogen content in the waste water and has excellent environment-friendly benefits.

Description

A kind of recovery method of ammonium salt

Technical field:

The present invention relates to a kind of ammonium salt NH ₄The recovery method of X is meant a kind of ammonium salt or its aqueous solution more specifically, with the method for aromatic amine prepared in reaction free ammonia (amine) and fragrant amine salt.

Background technology:

Alkylated reaction is one of organic preparation feedback of most widely used preparation.In the alkylating reagent commonly used haloalkane (particularly alkyl chloride, bromoalkane), alcohol, alkyl sodium sulfate ester etc. are arranged.For reaction is carried out smoothly, in alkylated reaction, need to add acid binding agent.Acid binding agent commonly used has: organic amine compound, ammonia (ammoniacal liquor) or Na ₂CO ₃, MgO etc. owing to will generate gas CO with acid-respons ₂And make troubles to use, the inconvenience on the MgO solid uses, therefore industrial acid binding agent commonly used has: organic amine compound, ammonia (ammoniacal liquor).When alkylated reaction obtains product, all can form the by product ammonium salt.To organic amine usually is to add mineral alkali to reclaim amine.To inorganic ammonia (ammoniacal liquor), then generate NH ₄X is because NH ₄The value of Cl etc. is on the low side, at present as direct discharging of waste water, brings the ammonia nitrogen problem thus.

When preparing ester or acid amides with acyl chlorides, also ammonium salt as by-product by usually, the NH of generation ₄X needs to recycle or processing treatment too.

At present, about NH ₄The recovery of X and decomposition, it is disclosed to have only a small amount of patent and document to have, as: Kessler just proposed NH as far back as nineteen twenty-nine ₄Cl gas is by the NH of molten state ₄HSO ₄In (220～270 ℃), discharge HCl gas; Continue to be warming up to more than 330 ℃ (NH ₄) ₂SO ₄Resolve into NH ₄HSO ₄And NH ₃, NH ₄HSO ₄Recycle; Patent USP4293532, JP58-161902 etc. are to NH ₄HSO ₄, (NH ₄) ₂SO ₄And NH ₄The method of stepwise reaction is improved behind the Cl blended melting, but all exists the temperature of reaction height, the problem that transformation efficiency is low, problem such as the stifled equipment of ammonium chloride distillation and can't industrialization.Proposition such as USP2823981 and CN1032418C utilizes MgO decomposing N H in the aqueous solution earlier ₄Cl obtains NH ₃And MgCl ₂6H ₂O, MgCl ₂6H ₂O is Mg (OH) Cl+HCl or further is decomposed into MgO+HCl at 600 ℃ at pyrolytic decomposition more than 350 ℃, and with the MgO cyclic utilization method that obtains, this method exists that to steam water yield big, and the energy consumption height takes off HCl temperature of reaction height, to problems such as equipment corrosion are serious.USP4305917 proposes to utilize organic amine decomposing N H in organic solvent ₄Cl obtains NH ₃And organic ammonium salt, distill out anhydrate and organic solvent after organic ammonium salt be heated to 100 ~ 250 ℃ of pyrolytic decompositions and obtain organic amine and HCl, this method exist equally steam the water yield, quantity of solvent is big, the energy consumption height, problem such as utilize boiling-point difference that organic ammonium salt is decomposited organic amine and HCl is very difficult, and transformation efficiency is very low.And most of aliphatics amine salt heat is temperature not, (as more than 120 ℃) problem with regard to occurring decomposing under higher slightly temperature.

Based on the problems referred to above, make the present invention.

Summary of the invention:

A first aspect of the present invention purpose is to provide a kind of decomposition temperature low, the ammonium salt recovery method of complete decomposition.The technical scheme that the present invention takes for achieving the above object is as follows:

A kind of recovery method of ammonium salt is characterized in that: at NH ₄X solid or NH ₄In the X aqueous solution, add aromatic amine and NH ₄The X reaction obtains fragrant ammonium salt and ammonia or ammoniacal liquor.

Ammonium salt recovery method of the present invention is applicable to NH ₄X solid or NH ₄The X aqueous solution, described NH ₄X is organic ammonium salt or inorganic ammonium salt, and organic ammonium salt comprises that the hydrogen atom in the ammonium ion is replaced the compound that generates by aliphatic hydrocarbon, aromatic hydrocarbon, and inorganic ammonium salt comprises NH ₄Cl, NH ₄Br, NH ₄The ammonium salt or their aqueous solution such as I.

The aromatic amine that the present invention adopts amido and aromatic group directly to link to each other.Ammonium salt there is good dissolving ability, thereby can effectively avoids NH ₄X such as NH ₄Bad phenomenon such as the equipment obstruction that the distillation of Cl, crystallization bring are preferably aniline, substituted aniline, mphenylenediamine, Ursol D, connect phenylenediamine, are with substituent phenylenediamine, naphthylamines, replacement naphthylamines or polycyclic aromatic hydrocarbons amine.

Further, after reaction is finished, steam free ammonia or ammoniacal liquor in 50 ~ 350 ℃, ammonia still process obtains free ammonia or ammoniacal liquor and fragrant ammonium salt after finishing.Wherein: the condensable compression system liquefied ammonia of the free ammonia that steams, also used water absorbs and makes ammoniacal liquor or other ammonium salt etc.The fragrance ammonium salt can directly apply to further reaction, as reactions such as the selectively acylating of diazotization reaction, fragrant ammonium salt, alkylations.

The present invention compared with prior art has following beneficial effect:

1, because there is NH in aromatic amine ₄The decomposition temperature that ammonia (ammoniacal liquor) is emitted in the X decomposition is low, complete decomposition.Aromatic amine dissolving NH ₄The ability of X is strong, therefore can effectively avoid NH ₄X such as NH ₄Bad phenomenon such as the equipment obstruction that the distillation of Cl, crystallization bring.

2, aromatic amine and NH ₄X among the X in conjunction with salify after, can be directly used in follow-up diazotization, the selective reaction of polyamines.Thereby reduce the eo-acid consumption of the required interpolation of protection aromatic amine.

3, aromatic amine and X bonded generate salt, Heat stability is good, at high temperature NH ₄The X decomposition is emitted in ammonia (ammoniacal liquor) process, the no decomposing phenomenon of fragrant ammonium salt itself, and the fragrant ammonium salt product purity that obtains is good.

4, tie up the ammonium salt-containing waste water that acid produces, can be used for regenerating ammoniacal liquor or recovery organic amine reduce the generation of waste water, lower the ammonia-nitrogen content of waste water.

The invention will be further described below in conjunction with embodiment.

Embodiment:

Embodiment 1:

With 18gNH ₄Cl solid and 45ml water add in the 150ml flask, and add mphenylenediamine 36g, use N ₂Gas or other rare gas element be the air displacement in the flask, is heated to 120 ℃ and boils off and steam the about 48g of ammoniacal liquor, continues to be warmed up to 220 ℃ of reactions 1 hour, steams the about 3g of ammonia.With the flask cooling, get mphenylenediamine mono-hydrochloric salts 48g.

The above-mentioned mphenylenediamine mono-hydrochloric salts 48g of adding and 35g Glacial acetic acid, water 24g are warmed up to 90～95 ℃ of insulation reaction 10 hours in the 150ml flask.Carry out the terminal point sampling then, detect with high pressure liquid chromatograph, its product purity is 93%.The material intermittent type is stirred cooling,, pour out suction filtration to below 35 ℃, washing, oven dry, product purity obtains 3-acetylaminoaniline 50g greater than 98%.

Embodiment 2:

With 32gNH ₄The Cl solid adds in the 150ml flask, and adds 2, and 4-diamino anisole 82g uses N ₂Gas or other rare gas element be the air displacement in the flask, is heated to 160 ℃ of reactions 3 hours, and will steam the ammonia water absorb 10% the about 100g of ammoniacal liquor, with the flask cooling, must 2,4-diamino anisole mono-hydrochloric salts 104g.

In the 500ml flask, add above-mentioned 2,4-diamino anisole mono-hydrochloric salts 104g, add Glacial acetic acid 45 g, oil bath is warmed up to 70～75 ℃ of insulation reaction 1 hour, is warmed up to 80～85 ℃ of insulation reaction 2 hours, is warmed up to 90～95 ℃ of insulation reaction 15 hours.Carry out the terminal point sampling then, detect with high pressure liquid chromatograph, its product purity is 93%.The material intermittent type is stirred cooling,, pour out suction filtration to below 35 ℃, washing, oven dry, product purity surpasses 98%, weight 132g.It is dissolved in the 200ml water, uses Na ₂CO ₃Transfer pH to 8, branch vibration layer is used the 50ml water washing once again, gets 2-methoxyl group-5-acetylaminoaniline 108g.

Embodiment 3:

With 32gNH ₄The Br solid adds in the 500ml flask, and adds aniline 30g, uses N ₂Gas or other rare gas element be the air displacement in the flask, is warmed up to 180 ℃ of reactions 5 hours, the ammonia water that obtains absorb 10% the about 55g of ammoniacal liquor.Get aniline salt 57g in the still.

The cooling back adds 30% hydrochloric acid 2ml water 50ml, when cooling to 5 ~ 10 ℃, drips sodium nitrite in aqueous solution in reactor.With the excessive nitrous acid of starch potassium iodide paper check, to determine reaction end.After diazotization finishes, in system, add the condenses 160g of H acid and cyanuric chloride, during use Na ₂CO ₃Hierarchy of control pH value is 5, reacts 1 hour, adds urea 30g, and controlling the pH value again is 7, reacted 10 hours, and be terminal point with the diazonium salt disappearance.The common salt aqueous solution 150ml of adding 25% stirs, and control pH value is 7, filters.In oven dry below 85 ℃, get reactive brilliant red x-3b dyestuff 200g.

Embodiment 4:

With 10gNH ₄The Cl solid adds in the 500ml flask, and adds 2-amino-6-methoxyl group-benzothiazole 30g, and water 150 ml are warmed up to 80 ℃ of reactions 5 hours, and distillation ammoniacal liquor obtains about 2% the about 135ml of ammoniacal liquor.Obtain corresponding amine salt 37g in the still.

The cooling back adds 30% hydrochloric acid 1ml water 50ml, when cooling to 5 ~ 10 ℃, drips sodium nitrite in aqueous solution in reactor.With the excessive nitrous acid of starch potassium iodide paper check, to determine reaction end.After diazotization finishes, add 8-hydroxyl-3,4 naphtho-(3 '-hydroxyl) tetrahydropyridine 35g in system, stirring reaction 1 hour is a terminal point with the diazonium salt disappearance, filters.Add with 100g water and 100g ice stirring reaction 10 hours, add 35% the liquid caustic soda neutrality that neutralizes, with the dilution of 500ml water, filtration, grinding, dry EX-SF DISPERSE BLUE EX-SF 300 5G product 70g.

Embodiment 5:

With 30gNH ₄The Cl solid adds in the 500ml flask, and adds 2-naphthylamines 80g, is warmed up to 280 ℃ of reactions 1 hour, the ammonia water that obtains absorb 10% the about 55g of ammoniacal liquor.Get naphthylamines salt 98g in the still.

The cooling back adds 30% hydrochloric acid 2ml water 100ml, when cooling to 5 ~ 10 ℃, drips sodium nitrite in aqueous solution in reactor.With the excessive nitrous acid of starch potassium iodide paper check, to determine reaction end.Diazotization adds different types of coupler and carries out coupled reaction after finishing, and prepares multiple dyestuff.

As can be seen from the above-described embodiment:

The present invention will be by containing NH ₄The waste water of X or its salt and aromatic amine compounds reaction; generate ammoniacal liquor and fragrant amine salt; the fragrant ammonium salt product purity that obtains is good; prepared fragrant ammonium salt; can be applicable to further diazotization reaction, in the reaction such as the selectively acylating of fragrant ammonium salt, alkylation, have very good prospects for commercial application; simultaneously, the present invention also provides a kind of and can effectively reduce NH ₄The method of the useless admittedly or waste water of X can reduce the ammonia-nitrogen content in the waste water, has environmental benefit very.

Embodiment 6:

With 20g (C ₂H ₅) ₃The NHCl solid adds in the 500ml flask, and adds dianisidine 18g, uses N ₂Gas or other rare gas element are with the air displacement in the flask, and it is 0.07MPa that the water environmental protection is evacuated down to vacuum tightness, be warmed up to 200 ℃ the reaction 3 hours, the triethylamine that obtains with cold well condensation after about 13g.Obtain corresponding amine salt 24g in the still.

The cooling back adds 30% hydrochloric acid 1ml water 50ml, when cooling to 5 ~ 10 ℃, drips sodium nitrite in aqueous solution in reactor.With the excessive nitrous acid of starch potassium iodide paper check, to determine reaction end.After diazotization finished, adding H acid sodium-salt 100g carried out coupled reaction in system, carries out condensation reaction with cyanuric chloride 50g afterwards, and reaction back and ammoniacal liquor reaction get reactive dark blue product 180g at last.

Claims

1. the recovery method of an ammonium salt is characterized in that: at NH ₄X solid or NH ₄In the X aqueous solution, add aromatic amine and react, use N ₂Gas or other rare gas element heat the air displacement in the flask, obtain fragrant ammonium salt and ammonia or ammoniacal liquor, described NH ₄X is NH ₄Cl or NH ₄Br, described aromatic amine are mphenylenediamine, aniline or 2-naphthylamines.

2 .The recovery method of a kind of ammonium salt according to claim 1 is characterized in that: after reaction is finished, steam free ammonia or ammoniacal liquor in 50 ~ 350 ℃, ammonia still process obtains free ammonia or ammoniacal liquor and fragrant ammonium salt after finishing.

3 .The recovery method of a kind of ammonium salt according to claim 2 is characterized in that: wherein: liquefied ammonia is made in the free ammonia condensation compression that steams, and perhaps water absorbs and makes ammoniacal liquor.

4 .The recovery method of a kind of ammonium salt according to claim 2 is characterized in that: prepared fragrant ammonium salt is applied to the selectively acylating or the alkylated reaction of diazotization reaction, fragrant ammonium salt.