CN106831459A - The environment-friendly preparation method thereof of Iminodiacetate in a kind of near-critical water - Google Patents
The environment-friendly preparation method thereof of Iminodiacetate in a kind of near-critical water Download PDFInfo
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- CN106831459A CN106831459A CN201611042782.0A CN201611042782A CN106831459A CN 106831459 A CN106831459 A CN 106831459A CN 201611042782 A CN201611042782 A CN 201611042782A CN 106831459 A CN106831459 A CN 106831459A
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- iminodiacetonitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/26—Carbonates or bicarbonates of ammonium
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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Abstract
The invention discloses a kind of environment-friendly preparation method thereof of Iminodiacetate in near-critical water, belong to fine-chemical intermediate preparing technical field.The technical problems to be solved by the invention：Production technology is convenient, yield is higher, product quality is preferable and environmentally safe.Technical characterstic：Iminodiacetonitrile than is uniformly mixed with alkali carbonate with the amount of a certain amount of material, it is added in the stainless steel intermittent reaction formula device equipped with water, or the aqueous solution of the mixture is flowed through into tubular reaction device, 240 ~ 250 DEG C of control reaction unit external temperature, 6 ~ 8 minutes reaction time, 7 ~ 10MPa of system pressure；Promote the carrying out of hydrolysis, and final products obtained therefrom mixed liquor using the near critical characteristic of aqueous carbonate salt system；By resulting solution through decolourize, concentration, crystallization, dry can anhydrous solid product.The present invention prepares Iminodiacetate by means of near-critical water carbonate system, using more gentle additive accelerator, decolourizes simple, and water used can be recycled.
Description
Technical field
The invention belongs to fine-chemical intermediate preparing technical field, it is related to iminodiacetic acid in a kind of near-critical water
The environment-friendly preparation method thereof of salt.
Background technology
Iminodiacetate is a kind of important fine-chemical intermediate, and its property is compared with iminodiacetic acid stabilization, profit
In storage and transport, it is widely used in the fields such as agricultural chemicals, fuel, medicine, synthetic resin, water process and electronic apparatus.At present,
The preparation method of Iminodiacetate is more, mainly includes：Chloroactic acid method, amion acetic acid method, nitrilotriacetic acid method and hydrogen cyanogen
The hydrolysis of acid system, wherein iminodiacetonitrile is one of common method.Iminodiacetonitrile and highly basic are mixed in certain proportion,
Hydrolytic reaction pot is added to, controls certain reaction temperature to can be obtained by required product, but the product for directly obtaining with the time
Product color is relatively deep, it is necessary to be decolourized to it.The effect on driving birds is not good if direct bleaching allows it with list, it is necessary to adjust its pH value with acid
Salt form presence is decolourized again, and this process need to consume substantial amounts of acid, and production cost is also increased while being polluted to environment, grind
Studying carefully pollution-free, the inexpensive green chemical industry synthesis technique of exploitation turns into the key problem of the technology path.
Green chemical technology is the emerging technology flourished over nearly 10 years, has extremely important application to carry on the back
Scape and wide application prospect, are that one kind prevents pollution from source, no longer produce waste, do not reprocess waste, final to realize
No pollution and the green technology of zero-emission.It is super（Closely）Critical technology is exactly the important green chemical technology of one of which.
Water as the most frequently used green medium of nature, because its wide material sources, it is inexpensive it is nontoxic, be easy to be separated from product,
It is widely used in green chemical industry field even without being removed from end product.The focus of research is concentrated mainly on supercritical water
（Refer to fluid of the temperature more than 374 DEG C of critical-temperature, pressure more than critical pressure 22.1MPa）And near-critical water（Refer to that temperature is in
150 ~ 370 DEG C, pressure is in the fluid of 0.4 ~ 22.1MPa）(document：Savage P E, Akiya N. Roles of water
for chemical reactions in high-temperature water, Chem Rev. 2002,102:2725-
2750).For supercritical water, main research direction is deep oxidation and organic chemical reactionses etc.；For near-critical water, mainly
It is applied to the aspects such as the renewable resources of waste treatment and discarded object.Near-critical water shows superior mass transfer as supercritical water
Performance, while having concurrently, dissociation constant is big and the small characteristic of dielectric constant, because reaction condition is gentleer, grasps with stronger
The property made, thus than supercritical water more suitable for the medium as organic reaction.In organic chemical reactionses both can as solvent,
Again can be as reactant and catalyst (document：Wang Xuan, Duan Peigao, wear vertical super (near) criticals of benefit in organic chemical reactionses
In application, chemistry circular .2005,68:W053).Many organic compounds can just be hydrolyzed in normal-temperature water, but must
There must be the addition of strong acid or alkali catalyst.The maximum advantage of near-critical water is that can reduce even to exempt strong acid or base catalyst
Use, while can by the conditions such as the temperature of control system, pressure come its pH value of modulation and be finally reached regulation and control reaction conversion
The purpose that rate is distributed with product.At present, smoothly realize the hydrolysis of acetates in near-critical water, and achieve compared with
Good conversion ratio and yield.Nitrile can equally be hydrolyzed as a kind of important organic chemical intermediates in near-critical water,
Hydrolysis first generates acid amides, further hydrolysis generation carboxylic acid.Iyer and Klein hydrolyze reaction power to butyronitrile in near-critical water
Carried out lot of experiments [document：Iyer S D, Nicol G R, Klein M T. Hydrothermal
reactions of 1-nitrobutane in high-temperature water. J Supercrit. Fluids.
1996,9:26-32]；Hydrolysis properties of the Kramer et al. to acetonitrile and benzonitrile in near-critical water have carried out system thinking, and
Determine corresponding kinetic constant [document：Krammer P, Vogel H. J Supercrit. Fluids. 2000,16:
932-935]；Dai LY etc. generate iminodiacetic acid with the hydrolysis that near-critical water system smoothly realizes iminodiacetonitrile
Research [document：Duan PG, Wang X, Dai LY. Noncatalytic hydrolysis of
iminodiacetonitrile in near-critical water-a green process for the
manufacture of iminodiacetic acid. Chem. Eng.&Technol. 2007, 30 (2): 265 -
269]。
The content of the invention
It is Iminodiacetate the invention provides Iminodiacetate environment-friendly preparation method thereof in a kind of near-critical water
The improvement of production technology provides a kind of technical strategies, simple to operation, decolourizes simple, and raw material availability is high, and cost is relatively low,
And used medium water can be recycled.
Particular technique route of the invention is mainly realized by following approach：
The hydrolysis of iminodiacetonitrile is realized as reaction system using near-critical water and alkali metal carbonate solution, generation is corresponding
Iminodiacetate.Comprise the following steps that：1. in intermittent reaction device Iminodiacetate preparation.By imino group
Diacetonitrile compares 1 with alkali carbonate with the amount of material：1 ~ 4 uniform mixing, is added to the intermittent reaction device equipped with water
In, with 2 ~ 4MPa of purity nitrogen pressurization, sealing is put into reaction unit in fuse salt, 200 ~ 250 DEG C of control salt temperature, and reaction 6 ~
10 minutes.Reaction terminates, and cooling, decompression pours out solution in reaction unit, filtering, decolourize, concentration, crystallization can imino-diacetic
Acetate solid.2. in continuous reaction apparatus Iminodiacetate preparation.By iminodiacetonitrile and alkali metal carbonic acid
Salt compares 1 with the amount of material：1 ~ 4 uniform mixing, is configured to the aqueous solution.It is set to flow through tubular type with certain flow rate with high-pressure plunger pump
Reaction unit, 200 ~ 250 DEG C of control reaction unit pipeline external temperature, 7 ~ 8MPa of pressure in counterbalance valve control pipeline, during stop
Between 6 ~ 10 minutes, efflux is Iminodiacetate solution, filtering, decolourize, concentration, crystallization can iminodiacetic acid
Salt solid.
The present invention has advantages below：
1. the use of alkali catalyst is avoided, and using more gentle catalyst additive, and the additive can be as anti-
Thing is answered to be transformed into product.
2. the near critical characteristic of sufficient resources water is made full use of, additive modulation is introduced simultaneously as reaction medium microcosmic
Reaction environment, improves reaction conversion ratio and yield, and the Iminodiacetate color of generation is shallower, it is easy to direct bleaching.
3. a large amount of water used by whole process can be recycled, and separating obtained accessory substance -- and ammonium carbonate can be as nitrogenous fertilizer
It is applied to agricultural production.
Brief description of the drawings
Fig. 1 is batch reactor structural representation
Fig. 2 is flow reactor structural representation
In Fig. 1：A- valves；B- explosion-proof valves；C- pressure gauges；D- agitators；E- temperature tubes；F- air inlets；G- gas outlets；H- is vented
Mouthful.In Fig. 2：1- water tanks;2,4,7,11,14,19,23,24- high pressure valves;5- mechanical agitators;6- slurry box; 3,
8- high-pressure plunger pumps;9- preheaters r;10- High Purity Nitrogen gas cylinder 12- thermocouples;13,17- safety valves;18- pressure gauges;
16- reactors;20- heat exchangers;21- counterbalance valves;22- gas-liquid separators.
Specific embodiment
Embodiment 1
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：1 uniform mixing, is added to the batch (-type) equipped with water
In reaction unit, with purity nitrogen pressurization 4MPa, sealing is put into reaction unit in fuse salt, and 240 DEG C of control salt temperature reacts 8 points
Clock, cooling, decompression pours out solution in reactor, filtering, decolourize, concentration, crystallization can the double salt solids of iminodiacetic acid, produce
Rate 60~65%.Backflow is carried out to product with the activated carbon of 2.5% (m/m) mass ratio to decolourize that colorless solid product can be obtained in 1 hour.
Embodiment 2
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：2 uniform mixing, are added to the batch (-type) equipped with water
In reaction unit, with purity nitrogen pressurization 4MPa, sealing is put into reaction unit in fuse salt, 240 DEG C of control salt temperature, reaction 6
Minute, cooling, decompression pours out solution in reactor, filtering, decolourize, concentration, crystallization can the double salt solids of iminodiacetic acid,
Yield 75~80%.Backflow is carried out to product with the activated carbon of 2.5% (m/m) mass ratio to decolourize that colorless solid product can be obtained in 1 hour.
Embodiment 3
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：4 uniform mixing, are added to the batch (-type) equipped with water
In reaction unit, with purity nitrogen pressurization 4MPa, sealing is put into reaction unit in fuse salt, 240 DEG C of control salt temperature, reaction 6
Minute, cooling, decompression pours out solution in reactor, filtering, decolourize, concentration, crystallization can the double salt solids of iminodiacetic acid,
Yield 85~90%.Backflow is carried out to product with the activated carbon of 2.5% (m/m) mass ratio to decolourize that colorless solid product can be obtained in 1 hour.
Embodiment 4
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：1 uniform mixing, is configured to the aqueous solution, uses high-pressure column
Plug pump makes the solution flow through pipe reaction device, 250 DEG C of control reaction unit pipeline external temperature, counterbalance valve control with certain flow rate
Tubing giving sufficient strength 7 ~ 8MPa of internal pressure, the residence time is 6 minutes, and efflux is the double salting liquids of iminodiacetic acid, filters, takes off
Color, concentration, crystallization can obtain the double salt solids of iminodiacetic acid, yield 65~70%.With the activated carbon of 2.5% (m/m) mass ratio
Backflow is carried out to product to decolourize that colorless solid product can be obtained in 1 hour.
Embodiment 5
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：2 uniform mixing, are configured to the aqueous solution, use high-pressure column
Plug pump makes it flow through pipe reaction device, 250 DEG C of control reaction unit external temperature, counterbalance valve control reaction dress with certain flow rate
Put 7 ~ 8MPa of internal pipe pressure, the residence time is 7 minutes, efflux is the double salting liquids of iminodiacetic acid, it is filtering, dense
Contracting, crystallization can obtain the double salt solids of iminodiacetic acid, yield 75~80%.With the activated carbon of 2.5% (m/m) mass ratio to product
Backflow is carried out to decolourize that colorless solid product can be obtained in 1 hour.
Embodiment 6
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：4 uniform mixing, are configured to the aqueous solution, use high-pressure column
Plug pump makes it flow through pipe reaction device, 250 DEG C of control reaction unit external temperature, counterbalance valve control reaction dress with certain flow rate
7 ~ 8MPa of internal pipe pressure is put, the residence time is 8 minutes, efflux is the double salting liquids of iminodiacetic acid, filters, takes off
Color, concentration, crystallization can obtain the double salt solids of iminodiacetic acid, yield 85-90%.With the activated carbon pair of 2.5% (m/m) mass ratio
Product carries out backflow and decolourizes that colorless solid product can be obtained within 1 hour.
Claims (9)
1. in a kind of near-critical water Iminodiacetate environment-friendly preparation method thereof, concrete operation step is as follows：
1）, in batch reactor Iminodiacetate preparation；
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：1~4 uniform mixing, is added to equipped between water
In formula of having a rest reactor, with 2~4MPa of purity nitrogen pressurization, sealing is put into reactor in fuse salt, control salt temperature 200~250
DEG C, to react 6~10 minutes, cooling is depressurized and pours out solution in reactor, and filtering, concentration, crystallization can obtain Iminodiacetate
Solid；Backflow decolouring is carried out to product with the activated carbon of 2.5% (m/m) mass ratio can obtain colorless solid product；
2）, in flow reactor Iminodiacetate preparation；
Iminodiacetonitrile and alkali carbonate are compared 1 with the amount of material：0.5~4 uniform mixing, is configured to the aqueous solution, uses
High-pressure plunger pump makes it flow through tubular reactor, 200~250 DEG C of control reactor external temperature, counterbalance valve control with certain flow rate
7~8MPa of pressure in tubing giving sufficient strength, the solution residence time in the reactor is 6~10 minutes, and efflux is iminodiacetic acid (salt)
Acid salt solution, filtering, concentration, crystallization can obtain Iminodiacetate solid；With the activated carbon of 2.5% (m/m) mass ratio to producing
Product carry out backflow decolouring and can obtain colorless solid product.
2., according to preparation method required in claims 1, required alkali carbonate is potassium carbonate and sodium carbonate.
3. according to preparation method required in claims 1, intermittent reaction device, iminodiacetonitrile and alkali metal salt
The amount ratio of material is 1：1 can generate the double salt of iminodiacetic acid, 240 DEG C of operation temperature, pressure 8MPa.
4. according to preparation method required in claims 1, intermittent reaction device, iminodiacetonitrile and alkali metal salt
The amount ratio of material is 1：2 generations are the double salt of iminodiacetic acid, 240 DEG C of operation temperature, pressure 8MPa.
5. according to preparation method required in claims 1, intermittent reaction device, iminodiacetonitrile and alkali metal salt
The amount ratio of material is more than 1：4 generations are the double salt of iminodiacetic acid, 240 DEG C of operation temperature, pressure 8MPa.
6. according to preparation method required in claims 1, continuous reaction apparatus, iminodiacetonitrile and alkali metal salt
The amount ratio of material is more than 1：1 generation is the double salt of iminodiacetic acid, 250 DEG C of operation temperature, 7~8MPa of pressure.
7. according to preparation method required in claims 1, continuous reaction apparatus, iminodiacetonitrile and alkali metal salt
The amount ratio of material is more than 1：2 generations are the double salt of iminodiacetic acid, 250 DEG C of operation temperature, 7~8MPa of pressure.
8. according to preparation method required in claims 1, continuous reaction apparatus, iminodiacetonitrile and alkali metal salt
The amount ratio of material is more than 1：4 generations are the double salt of iminodiacetic acid, 250 DEG C of operation temperature, 7~8MPa of pressure.
9. according to preparation method required in claims 1, for the decolouring of batch (-type) and flow-type products therefrom solution
Method is that the activated carbon of 2.5% (m/m) mass ratio is added in reaction mixture, is flowed back 1 hour at a temperature of 80~90 DEG C.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833563A (en) * | 2014-02-21 | 2014-06-04 | 重庆紫光化工股份有限公司 | Method for increasing yield of iminodiacetic acid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833563A (en) * | 2014-02-21 | 2014-06-04 | 重庆紫光化工股份有限公司 | Method for increasing yield of iminodiacetic acid |
Non-Patent Citations (4)
| Title |
|---|
| PEI-GAO DUAN ETAL: "Noncatalytic hydrolysis of iminodiacetonitrile in near-critical water - a green process for the manufacture of iminodiacetic acid", 《CHEM. ENG. TECHNOL.》 * |
| 段培高: "近临界水中腈、酰胺的水解反应研究", 《华东师范大学博士学位论文》 * |
| 段培高等: "近临界水自催化下亚氨基二乙腈水解反应研究", 《功能材料》 * |
| 王炫: "近临界水中自身碱催化有机反应的研究", 《华东师范大学硕士学位论文》 * |
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