CN105985251B - A kind of amino acids process for cleanly preparing such as iminodiacetic acid - Google Patents
A kind of amino acids process for cleanly preparing such as iminodiacetic acid Download PDFInfo
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Abstract
The present invention relates to the clean preparation methods of the amino acids such as iminodiacetic acid.Alkaline hydrolysis, deamination are carried out to amino nitrile using cheap milk of lime, iminodiacetic acid (salt) acid calcium salt crude product can be obtained.The iminodiacetic acid (salt) acid calcium salt crude product of gained can be suspended in water or mother liquor, and sulfuric acid is added or other are mineral acid acidified, filter out water-soluble small inorganic calcium salt filter cake.Filtrate cooling crystallization, separation can obtain iminodiacetic acid solid, and crystalline mother solution set is used for next group acidification reaction.Further gypsum can be converted to calcium carbonate and ammonium sulfate using the carbon dioxide in the ammonium hydroxide and flue gas of alkaline hydrolysis byproduct in process, directly generate composite fertilizer when being acidified with sulfuric acid；Also it may separate out calcium carbonate and concentrate out ammonia sulfate crystal；Calcium carbonate can be used as by-product sale or heat resolve goes out quick lime raw material and applies mechanically.New process can realize that the full utilization of resource, reaction selectivity higher reduce the generation of colored byproducts, it avoids concentration and removes the abraum salts such as sodium sulphate and sodium chloride process and wastewater treatment link, decolorising agent dosage can be greatly decreased in concentration, and energy-saving notable, production cost declines notable.
Description
Technical field
The present invention relates to the process for cleanly preparing of the amino acids such as iminodiacetic acid, belong to pesticide, chemical fertilizer and fining
Work technical field.
Background technology
Iminodiacetic acid, CAS 142-73-4, alias diglycinee, N- (carboxymethyl) glycine, ammonia oxalic acid,
Abbreviation IDA.Iminodiacetic acid is mainly used as the intermediate of the pesticides such as synthesizing glyphosate, while also being used as releasing the organic economic benefits and social benefits of phosphorus
The fertile, raw material of ion exchange resin and rubber, plating, food additives etc..
Iminodiacetic acid has following several synthesis routes：
1, chloroactic acid method monoxone reacts production sodium chloroacetate with ammonium hydroxide or sodium hydroxide, then is generated with hydration hydrazine reaction
Hydrazine embraces oxalic acid, is then acidified again with hydrochloric acid under sodium nitrite effect, generates iminodiacetic acid hydrochlorid, stand still for crystals,
Suction filtration, is dissolved in hot water pickling, and sodium hydroxide solution is added and is neutralized, that is, generates iminodiacetic acid.The method yield
Low, wastewater flow rate is big, complex steps, and the cost of raw material is high, has been eliminated.
2, diethanolamine method diethanolamine method is the synthesis technology of the exploitation nineties in the world, is main with diethanol amine
Raw material passes through high temperature in the presence of Cu-Ni alloy catalysts and sodium hydroxide（170℃）, it is with pressure（0.8 Mpa）Deamination, it is raw
At iminodiacetic acid sodium, then it is acidified synthesis of iminodiacetic acid.The method raw material diethanol amine is influenced very greatly by crude oil price, and
The brine waste of high concentration is difficult to handle, which is replaced by hydrogen cyanide method substantially.
3, the hydrogen cyanide method method is current mainstream production method both domestic and external.United States Patent (USP) US5,187,301 reports use
Hydroxyacetonitrile prepares iminodiacetonitrile, and Chinese patent CN1609112A is reported synthesizes imido with iminodiacetic acid disodium salt
Base oxalic acid.The iminodiacetonitrile intermediate of hydrogen cyanide synthesis, with sodium hydroxide hydrolysis, acidification, decoloration, crystallization detach
To iminodiacetic acid.There are alkaline hydrolysis yield losses and be also easy to produce coloring matter in the method, diacid yield only has 90% left side
The right side, the diacid waste water of a large amount of saliferous take concentration desalination, the method for evaporation condensate biochemical treatment again, high energy consumption, the quality of salt
Difference utilizes difficulty.Although the method for the Acid hydrolysis iminodiacetonitrile synthesis of iminodiacetic acid that we develop reduces pair
The use of product and sodium hydroxide avoids production waste water, has obtained valuable ammonium chloride, but there are subtractive process complexity,
It is separated by solid-liquid separation often, invests larger shortcoming.Therefore the low amino acid of simple for process, small investment, production cost is explored
Process for cleanly preparing is still valuable.
Invention content
The object of the present invention is to provide a kind of amino nitriles to prepare the ammonia such as iminodiacetic acid, glycine with milk of lime alkaline hydrolysis
The process for cleanly preparing of base acids.
We have found that amino nitrile, which uses, has decomposition and aggregation problem, shadow in sodium hydroxide alkali solution preocess under study for action
Ring yield and product appearance.The reason is that since sodium hydroxide solution alkalinity is too strong, can not effectively inhibit controlling temperature
It decomposes the side reaction that raw material generates hydroxyacetic acid and glycine and formaldehyde and hydrogen cyanide polymerization generates coloring matter.
The present invention provides a kind of, and using alkalinity and solubility ratio sodium hydroxide solution, small, cost is only that sodium hydroxide five divides
One of the calcium hydroxide of left and right substitute sodium hydroxide alkaline hydrolysis carried out to iminodiacetonitrile, can get water-soluble smaller imino group
Oxalic acid calcium can carry out detaching or being directly acidified it with inorganic acids such as sulfuric acid, isolate water-soluble low inorganic calcium salt filter cake,
The method that the crystallization that cools down obtains iminodiacetic acid.
Specifically, the method that the present invention provides a kind of amino acid clean manufacturings such as iminodiacetic acid, this method include with
Lower step：
（1）Product, raw material or the mother liquor of imido- diacetonitrile and/or aminoacetonitriles, reaction are added into milk of lime
After 0.5-3 hours, deamination and control deamination terminal pH containing ammonia vapor be 8-9 isolate imino-diacetic through being filtered, washed
Calcium acetate crude product filter cake, alkaline hydrolysis mother liquor and wash water adjust sour acidizing crystal as quick lime water recycled or directly；
（2）By step（1）The crystallization of water or iminodiacetic acid is added in the iminodiacetic acid calcium crude product filter cake of middle gained
It is dispersed with stirring in mother liquor, sulfuric acid or other mineral acid acidified is added, filter out water-soluble small inorganic calcium salt filter cake, washing filter
Cake, washing lotion merge the material for next group diluting concentrated sulfuric acid or other inorganic acids, and filtrate is imido- diethyl acid solution；
（3）By step（2）The filtrate of middle gained cools down, and stirs lower crystallization, filters, washing, gained filter cake is imino-diacetic
Acetic acid crystal, crystalline mother solution recycled is in step（2）In.
2. according to the method described in claim 1, wherein,
Iminodiacetic acid calcium crude product is suspended in the ammonium hydroxide of by-product with the gypsum byproduct that sulfuric acid is acidified and is passed through two
The ammonium hydroxide that carbonoxide and alkaline hydrolysis workshop section generate is converted, and after reaction terminates, is filtered, washing, obtained solid is calcium carbonate；Filter
Liquid cool down or concentrate it is crystallizable isolate ammonium sulfate, mother liquor continues to apply mechanically；The gypsum of generation or the carbon of the generation further converted
Sour calcium-ammonium sulfate reaction mixture can not also detach, directly as composite fertilizer material.
3. according to the method described in claim 1, wherein, in step（1）In, iminodiacetonitrile or aminoacetonitriles and
The mass ratio of calcium oxide is 1:0.1-1.0, reaction temperature are 50-90 DEG C；Reaction solution deamination temperature is controlled at 70-105 DEG C.
4. according to the method described in claim 1, wherein, in step（1）In, lime can be digested with clear water, or with containing
There is the alkaline hydrolysis mother liquor of sodium sulphate, the aqueous solution of potassium sulfate or last consignment of to digest.
5. according to claim 1-4 any one of them methods, wherein in step（2）In, sulfuric acid or other inorganic acids
Total acid content and iminodiacetic acid calcium crude product in the molar ratio of iminodiacetic acid be 0.5-3：1, acidification terminal pH is 2,
The temperature of acidification is 50-105 DEG C, and acidificatoin time is 0.5 h-5 h.6. according to claim 1-5 any one of them methods,
Wherein, in step（2）In, the sulfuric acid amount being added in gypsum wash water is advisable with the desired amount of 30%-50% of next group acidification reaction,
Wash temperature is controlled at 60 DEG C or more.
7. according to the method described in claim 2, wherein, reaction temperature is 30-70 DEG C, reaction time 0.5-5h.
8. according to the method described in claim 1, the material after alkaline hydrolysis deamination can be directly acidified without isolation, isolate
After slightly solubility inorganic calcium salt, amino acid products, mother liquid recycle are crystallized out.
9. according to the method described in claim 1, isolating the acidification of the filtrate tune acid after iminodiacetic acid calcium solid
Terminal is the isoelectric point of orresponding amino acid.
Below by taking iminodiacetonitrile prepares iminodiacetic acid as an example, the present invention is described in detail.
In step（1）In, the reactive chemistry formula using calcium hydroxide alkaline hydrolysis iminodiacetonitrile is as follows：
During the alkaline hydrolysis, addition sequence, reaction temperature of raw material etc. have a direct impact the composition of alkaline hydrolysis product,
How to optimize reaction condition is the key point for realizing alkaline hydrolysis.
Reacting the thermal energy that generation calcium hydroxide is released with water using quick lime can make whole system temperature reach 50-60 DEG C
The temperature needed when reaction, then input iminodiacetonitrile, alkaline hydrolysis 0.5-3 h can make the iminodiacetonitrile in solution by several times
Reaction completely.If according to other patents（Publication number：CN101619077A）Method, substep puts into lime and iminodiacetic acid (salt)
Nitrile can cause the impurity contents such as nitrilotriacetic acid and glycine in product significantly to increase, wherein：The mass fraction of nitrilotriacetic acid
It is increased to 3.2% by being not detected for present invention process, the mass fraction of glycine is increased to by being not detected for present invention process
0.09%.Should the result shows that, substep puts into lime and iminodiacetonitrile, and, calcium content high equivalent ionic strong by reaction solution alkalinity is imitated
The influence answered, what lime was reacted with water is suppressed, and causes the alkaline hydrolysis time partially long（4-6 h）, by-product increase.Follow-up study is sent out
It is existing, if a small amount of ammonia of remaining, deamination terminal point control, in 8-9, may make impurity nitrilo three in the pH of steam containing ammonium hydroxide in reaction solution
Calcium acetate calcium glycine is dissolved in mother liquor, and the iminodiacetic acid calcium of the overwhelming majority is precipitated in solid form；If according to
The method of other patents（Publication number：CN101619077A）, deamination terminal can be used as with steam condensate (SC) weakly acidic pH, can cause to produce
The mass fraction of nitrilotriacetic acid is increased to 0.7% by being not detected for present invention process in product, and the mass fraction of glycine is by this hair
Being not detected for bright technique is increased to 0.09%.Should the result shows that, deamination terminal point control in 8-9, can avoid nitrogen in the pH of steam containing ammonium hydroxide
River triacetic acid calcium and calcium glycine impurity are precipitated out together with iminodiacetic acid calcium, are conducive to next step mother liquid recycle.
We have found that the presence containing sulfate radical substance such as sodium sulphate, potassium sulfate in milk of lime, can promote imino group
The alkaline hydrolysis and deamination speed of diacetonitrile.
Further investigation revealed that the solubility with temperature variation of iminodiacetic acid calcium is little, heat filtering can be carried out,
It is refiltered after need not cooling down.
For step（2）, it has been found that the total acid content of the sulfuric acid of addition or other inorganic acids and iminodiacetic acid calcium are thick
The molar ratio of iminodiacetic acid in product can control 0.5-3：1.When using sulfuric acid acidification, the sulfuric acid heat of hydration and reaction heat can
To be concentrated by evaporation out part water vapour, is adjusted convenient for temperature and water balance is adjusted, be acidified 0.5-5 h at this temperature, you can make
All iminodiacetic acid calcium are fully converted to iminodiacetic acid.Specific reactive chemistry formula is as follows：
20% or so iminodiacetic acid is entrained in filtering gained gypsum crude product, to avoid washing stone with a large amount of hot water
Cream increases concentration load, influences water balance.It can be used in wash water or in applying mechanically wash water, next batch reaction dosage 30%-50% be added
Inorganic acid hot acid water washing gypsum, the washing lotion of separation adds remaining inorganic acid for next group acidification reaction.Washing
Temperature is controlled at 50 DEG C or more, the solubility of iminodiacetic acid in water on the one hand can be improved, on the other hand when using sulphur
Calcium bisulfate precipitation can be generated when acid acidification to avoid gypsum and sulfuric acid reaction.
For step（3）, research finds that the solubility of iminodiacetic acid has the characteristic that is reduced with the reduction of temperature,
Such as：At 20 DEG C, solubility is 2.6 g in water, is 9.73 g at 50 DEG C, and 80 DEG C of whens are 23.8 g, and 100 DEG C of whens are 50 g.
The case where being applied mechanically in view of energy saving and mother liquor, we have selected acidification at boiling temperature to obtain iminodiacetic acid~stone
Lotion system heat filtering, hot filtrate is cooling to be water-cooled to 50 DEG C hereinafter, simultaneously at least 2 h or more of stirred crystallization at this temperature, with
Abundant crystallization is convenient for filtering, and by filtering, washing can obtain iminodiacetic acid crystals.
Gained crystallization filtrate can apply mechanically and next group acidification reaction.If color can use activity deeply partially after filtrate is applied mechanically repeatedly
Carbon decoloring is continuing with.
The method of other patents（CN101619077A）The mixing of the concentrated sulfuric acid and hydrochloric acid taken is acidified so that imino-diacetic
Acetic acid is in the method for hydrochloride form and Separation of gypsum.A large amount of concentrated mother liquors are not only needed, are frequently decolourized, Iminodiacetate
The glycine and nitrilotriacetic acid contained in acid salt solution, can cause the decline of pmida yield and quality, and lower mother liquor
Apply mechanically number.
The present invention uses alternating temperature crystallization and mother liquid recycle scheme, avoids a large amount of concentrated mother liquors, base compared with the prior art
Originally decoloration is avoided, processing step is simplified, can be reduced investment outlay, energy consumption can be greatly reduced, significantly reduces production cost, is realized clear
Clean production..
Due to during iminodiacetonitrile alkaline hydrolysis can a large amount of ammonias of by-product, this part ammonia it is recyclable as front or its
The raw material of its product.Use the gypsum of sulfuric acid acidification iminodiacetic acid calcium by-product as cement, gypsum board raw material, it can also be nearby
For salt-soda soil or acid soil improvement.In order to solve the outlet and storage transportation problem of by-product ammonium hydroxide, for a large amount of acid soils
Earth is improved and the needs of emission reduction, can be converted into calcium carbonate and ammonium sulfate as composite fertilizer material.For this purpose, we have developed one kind
Utilize the ammonia and gypsum of production iminodiacetic acid byproduct in process, production calcium carbonate, ammonium sulfate and calcium carbonate-ammonium sulfate
The method of composite fertilizer：By step（2）Gypsum crude product after middle sulfuric acid scrubbing adds suitable quantity of water to stir, and is passed through rich carbonated
The ammonia that flue gas and alkaline hydrolysis workshop section generate, 45-55 DEG C of 2 h of reaction, is filtered, washing, obtains calcium carbonate solid, and drying can be used as
Commodity.Filtrate concentrates or cooling may separate out ammonia sulfate crystal, and mother liquor continues to apply mechanically；Reaction mixture feed liquid can not also detach,
Produce calcium carbonate-sulfuric acid ammonium compound fertilizer.
In conclusion new process realizes the target that the quick alkaline hydrolysis of milk of lime prepares iminodiacetic acid calcium in high yield, mistake
Our the also ingenious reaction heat released in lime, the hydration heat of sulfuric acid and sulfuric acid acidization that are utilized carry out body in journey
System's heating and concentration, are greatly reduced energy consumption, by by-product gypsum, avoid mother liquor concentrations and desalination problem；By applying mechanically and
Alternating temperature crystallization strategy, greatly reduces iminodiacetic acid crystallization energy consumption, and mother liquor can recover system, again avoid traditional work again
Concentration energy consumption in skill and diacid loss；The gypsum of by-product can be used as byproduct direct marketing；Titanium dioxide more than needed can also be utilized
The ammonia of carbon and alkaline hydrolysis workshop section by-product is further converted to raw material or fertilizer.
Therefore, new process fundamentally overcomes the deficiency of prior art, has got rid of the link of concentration desalination, has reduced work
Property carbon decoloring number, saved a large amount of thermal energy and cold energy, improve product yield, it is suppressed that by-product generates, and has reached aobvious
Write energy-saving and clean manufacturing target.
Specific implementation mode
1 milk of lime of embodiment hydrolysis iminodiacetonitrile prepares iminodiacetic acid calcium
Xiang Shui（200 g）Middle input lime（31.4 g, 98%, 0. 55 mol）, it is stirred to react 15 min.Keep solution temperature
Iminodiacetonitrile is added at 50 DEG C or so in degree by several times（50 g, 95%, 0.5 mol）, or so half an hour finishes.At 50-55 DEG C
0.5-1 h are stirred, are warming up to 90-100 DEG C or so, depressurize deamination, and in due course moisturizing stops when the vapor pH steamed is in 8-9
Anti-avulsion ammonia.Filtering solution, washing.
Test to obtain iminodiacetic acid calcium crude product（113 g, imido- oxalic acid：58 g,1Have no that other are miscellaneous on H-NMR
Matter）, filtrate merging washing lotion（Imido- oxalic acid：5.2 g）, iminodiacetic acid calcium total recovery is 95.0%.
2 milk of lime of embodiment hydrolysis iminodiacetonitrile prepares iminodiacetic acid calcium, mother liquid recycle
Xiang Shui（60 g）Middle input lime（31.4 g, 98%, 0. 55 mol）, 15 min are stirred to react, add one
Mother liquor after the separation calcium salt of batch.It keeps solution temperature at 50 DEG C or so, iminodiacetonitrile is added by several times（50 g, 95%,
0.5 mol）, or so half an hour finishes.0.5-1 h are stirred at 50-55 DEG C, are warming up to 90-100 DEG C or so, depressurize deamination, and fit
When moisturizing, when the vapor pH steamed is in 8-9, stop deamination.Iminodiacetic acid calcium is filtered out, is washed, wash water merges female
Liquid set is reacted for next group.
Experimental result indicates that iminodiacetic acid total recovery is in 7 batch reaction iminodiacetic acid calcium crude products as follows
93.10%, the IDA in final mother liquor fold rate 2.26%, and 7 batch reaction iminodiacetic acid total recoverys are 95.50%.
3 patent of embodiment（Publication number：CN101619077A）Method prepares iminodiacetic acid calcium
In the reactor plus 872 mL of water, it is evacuated to 0.1 Mpa, is warming up to 45-50 DEG C, by lime（70%, 143 g）
And iminodiacetonitrile（95%, 151 g）It being uniformly added into water several times, every 5 min adds 1 time, and 3 h are finished, 1 h of insulation reaction,
It is warming up to 75 DEG C, 2 h of insulation reaction again, then is warming up to 100 DEG C, insulation reaction, until reaction is terminated when vapor pH is 7, it is cooling,
Filtrate and filter cake are collected in filtering respectively.
Test to obtain iminodiacetic acid calcium crude product（117 g, imido- oxalic acid：58.8 g, impurity：Nitrilotriacetic acid：
3.8 g, glycine：0.1 g）, filtrate merging washing lotion（Imido- oxalic acid：3.53 g）, iminodiacetic acid total recovery is
93.8%。
Compared to embodiment 1, the method prepares iminodiacetic acid calcium, and the reaction time is long, in product containing nitrilotriacetic acid,
The impurity such as glycine.
4 milk of lime of embodiment hydrolyzes iminodiacetonitrile, and deamination terminal point control is in pH=7 of vapor
Xiang Shui（200 g）Middle input lime（31.4 g, 98%, 0. 55 mol）, it is stirred to react 15 min.Keep solution temperature
Iminodiacetonitrile is added at 50 DEG C or so in degree by several times（50 g, 95%, 0.5 mol）, or so half an hour finishes.At 50-55 DEG C
0.5-1 h are stirred, are warming up to 90-100 DEG C or so, depressurize deamination, and in due course moisturizing stops as the vapor pH=7 steamed
Anti-avulsion ammonia.Filtering solution, washing.
Test to obtain iminodiacetic acid calcium crude product（118 g, imido- oxalic acid：60 g, nitrilotriacetic acid 0.8 g are sweet
Propylhomoserin：0.1 g）, filtrate merging washing lotion（Imido- oxalic acid：3.0 g, 0.8 g of nitrilotriacetic acid, glycine：0.5 g）,
Iminodiacetic acid total recovery is 95.0%.
Compared to embodiment 1, if deamination terminal point control can lead to the impurity such as nitrilotriacetic acid and Asia in pH=7 of vapor
Aminodiacetic acid calcium is precipitated together.
The solubility of 5 iminodiacetic acid calcium of embodiment at different temperatures
We have detected under different temperatures, the solubility of iminodiacetic acid calcium in water, the results show that solubility is with temperature
The variation of degree is little, stablizes in 1 g or so.
The solubility of 6 iminodiacetic acid of embodiment at different temperatures
We have detected under different temperatures, the solubility of iminodiacetic acid in water, the results show that solubility with temperature
Raising and increase.
7 sulfuric acid of embodiment is acidified iminodiacetic acid calcium
By iminodiacetic acid calcium crude product（35 g, 20 g of imido- oxalic acid）It is added to the water（100 g）, stir lower drop
Add sulfuric acid（98%, 15.1 g）, keep 95-100 DEG C of reaction 1h, concentration, total volume is in 125mL or so before keeping filtering, mistake while hot
Filter.The filtrate of detection gained and filter cake respectively.
Experimental result is shown, 14.5 g of iminodiacetic acid, yield 72.5% are contained in filtrate；Carry imido in filter cake secretly
5.5 g of base oxalic acid；Overall yield of reaction is more than 99%.
8 dilution heat of sulfuric acid of embodiment washs gypsum crude product
By sulfuric acid（98%, 5 g）Wash water is added（25 g）In, 70 DEG C are warming up to, the filter cake in embodiment 7 is washed, is filtered,
Filter cake clear water（5 g）Washing.5.4 g of imido- oxalic acid in filtrate；23.5 g of weight after filtration cakes torrefaction, with CaSO4·
0.5 H2O counts yield and is more than 99%, and the iminodiacetic acid of entrainment is less than 0.05 g.
9 iminodiacetic acid (salt) acid solution of embodiment cooling crystallization prepares iminodiacetic acid
By gained filtrate in embodiment 7（170 g, 14.5 g of imido- oxalic acid）, stirring, which declines, to be warmed to room temperature, and
2 h of crystallization at room temperature is filtered, washing, wash water merging filtrate（157 g, 3.5 g of imido- oxalic acid）.Filtration cakes torrefaction,
Smashing weighs to obtain 11.8 g of iminodiacetic acid, content 99.5%.
10 sulfuric acid of embodiment is acidified iminodiacetic acid calcium, after filtrate crystallization, recycled
By iminodiacetic acid calcium crude product（35 g, imido- oxalic acid 20g）It is added to the water（100 g）, stir lower drop
Add sulfuric acid（98%, 15.1 g）, 95-100 DEG C of 1 h of reaction is kept, concentrates excessive moisture, total volume is in 125-150 before keeping filtering
ML or so is filtered while hot.Filtrate stirring, which declines, to be warmed to room temperature, and water is used in 2 h of crystallization at room temperature, filtering（15 g）Washing 2
Secondary, 1 wash water is for washing gypsum crude product, 1 wash water of 2 wash waters as next group product.Product drying, smashing are weighed.
Crystalline mother solution set is used for next group acidification reaction.
By sulfuric acid（98%, 5 g）Product wash water and clear water is added（20-25 g）In, 70 DEG C are warming up to, filter cake, mistake are washed
Filter, filter cake clear water（5 g）Washing 2 times, 1 wash water is merged into cleaning solution, 1 wash water of 2 wash waters as next group gypsum.
Merge cleaning solution and clear water, remaining sulfuric acid is added, is used for the acidification of next batch reaction.Last batch of gypsum uses a large amount of hot water
Washing, washing lotion are merged into crystalline mother solution.
The iminodiacetic acid crystalline mother solution of last time（140 g, imido- oxalic acid：10.89 g）, activity is added
Charcoal（0.6 g）, 80 DEG C are warming up to, stirs 1 h at this temperature, it is cooling, it filters, washing.Crystalline mother solution color can be turned by black
Become light brown.The most moisture of concentration, dry obtained solid obtain iminodiacetic acid（11.5 g, purity 95.1%）.It is living
Property charcoal washed repeatedly with dilute hydrochloric acid solution, detect washing lotion in 0.21 g of imido- oxalic acid.
Experimental result shows, 7 batches of acidification reaction iminodiacetic acid product yields 97.4%, in conjunction with the embodiments 2 as a result,
It is hydrolyzed through lime by iminodiacetonitrile, sulfuric acid acidification, the total recovery for being prepared into iminodiacetic acid is：90.7%, sulfate hemihydrate
The total recovery of calcium is more than 99%.
11 gypsum crude product of embodiment prepares ammonium sulfate and calcium carbonate
By gained gypsum crude product in embodiment 8（30 g, 23.5 g containing half-H 2 O calcium sulphate）With water（30 g）Mixing is warming up to
45-55 DEG C, ammonia and carbon dioxide are passed through to solution under stirring.After reacting 1.5-2 h, acquired solution is obtained through filtering, concentration
Ammonia sulfate crystal（18.2 g）, yield 85.1%；After filtration cakes torrefaction, calcium carbonate powder is obtained（15.3 g, 13.8 g of calcium carbonate,
7.8 μm of average grain diameter）；Solution can not also detach, and be directly concentrated and dried, can obtain ammonium sulfate-compound of calcium carbonate（36 g, sulfur-bearing
18.2 g of sour ammonium, 13.8 g of calcium carbonate）.
12 lime of embodiment+sodium sulphate hydrolysis iminodiacetonitrile prepares iminodiacetic acid calcium
To input lime (31.4g, 98%, 0.55 mol) in water (200g) and anhydrous sodium sulfate (85.2g, 99%,
0.65mol), 15 min are stirred.50 DEG C or so are maintained the temperature at, iminodiacetonitrile (50g, 95%, 0.5 is added by several times
Mol), or so half an hour finishes.50-55 DEG C of stirring 0.5-1 h, is warming up to 90-100 DEG C or so, depressurizes deamination 1-2 hours, when
Vapor pH is steamed in 8-9, stops deamination.Filtering solution, washing.
Experiment obtains iminodiacetic acid calcium crude product (100.9g, imido- oxalic acid：48.1g,1It is had no on H NMR
Other impurities), filtrate merges washing lotion (imido- oxalic acid：16.4g), the total recovery of iminodiacetic acid is 96.9%.
13 lime of embodiment+a small amount of sodium sulphate hydrolysis iminodiacetonitrile prepares iminodiacetic acid calcium
To input lime (31.4g, 98%, 0.55 mol) in water (200g) and anhydrous sodium sulfate (7.2g, 99%,
0.055mol), 15 min are stirred.50 DEG C or so are maintained the temperature at, iminodiacetonitrile (50g, 95%, 0.5 is added by several times
Mol), or so half an hour finishes.50-55 DEG C of stirring 0.5-1 h, is warming up to 90-100 DEG C or so, depressurizes deamination 1-2 hours, when
Vapor pH is steamed in 8-9, stops deamination.Filtering solution, washing.
Experiment obtain iminodiacetic acid calcium crude product (86.9g, imido- oxalic acid 47.8g,1It is had no on H NMR
His impurity), filtrate merges washing lotion (imido- oxalic acid 15.8g), and the total recovery of iminodiacetic acid is 95.7%.
14 milk of lime of embodiment hydrolysis iminodiacetonitrile reaction mixture prepares iminodiacetic acid calcium
To the reaction mixture 50g of iminodiacetonitrile（Iminodiacetonitrile is 9.9g, aminoacetonitriles 0.7g, ammonia three
Acetonitrile is 0.5g, hydroxyacetonitrile 0.8g, ammonium sulfate 6.2g）Middle input 13.6g lime, maintains the temperature at 50-55 DEG C or so
Stirring 2 hours is warming up to 90-100 DEG C or so, depressurizes deamination, and in due course moisturizing stops when normal vapor pH is in 8-9
Anti-avulsion ammonia.Filtering solution washs solid.
Experiment obtain iminodiacetic acid calcium crude product (24.3g, imido- oxalic acid 11.7-g,1It is had no on H NMR
His impurity), filtrate merges washing lotion (119.7-g, imido- oxalic acid 1.6-g), and the total recovery of iminodiacetic acid is
95.8%。
15 lime of embodiment+sodium sulphate alkaline hydrolysis prepares glycine
To 40 DEG C of ammonium hydroxide 83.5g, 25.0%, 1.23mol) in be added hydroxyacetonitrile (50.0g, 40.1%,
0.35mol).It is stirred to react 1h at 50 DEG C, which is added lime（9.8g, 98%, 0.175mol）And sodium sulphate
In (12.5g, 99.0%, 0.09mol) mixed aqueous solution, 70 DEG C of alkaline hydrolysis 2h are warming up to 100 DEG C or so decompression deaminations, when steaming
Vapor pH=8-9 when, stop deamination.Filtering, washing, merging filtrate and wash water.
Filtrate merges washing lotion (111.8g, imido- oxalic acid 4.4g, glycine 19.4g, nitrilotriacetic acid 0.5g, hydroxyl
Guanidine-acetic acid 0.9g), filter residue (13.3g, imido- oxalic acid 0.2g, glycine 0.1g, nitrilotriacetic acid and hydroxyacetic acid nuclear-magnetism
It is not detected).
Claims (9)
1. a kind of amino acid clean preparation method such as iminodiacetic acid, this approach includes the following steps：
(1) product, raw material or the mother liquor of imido- diacetonitrile and/or aminoacetonitriles are added into milk of lime, reaction 0.5-3 is small
Shi Hou, deamination and control deamination terminal pH containing ammonia vapor be 8-9 it is thick to isolate iminodiacetic acid calcium through being filtered, washed
Product filter cake, alkaline hydrolysis mother liquor and wash water adjust sour acidizing crystal as quick lime water recycled or directly；
(2) the iminodiacetic acid calcium crude product filter cake of gained in step (1) is added to the crystalline mother solution of water or iminodiacetic acid
In be dispersed with stirring, sulfuric acid acidification is added, filters out water-soluble small inorganic calcium salt filter cake, washs filter cake, washing lotion merging is used for down
The material of a collection of diluting concentrated sulfuric acid, filtrate are imido- diethyl acid solution；
(3) filtrate of gained in step (2) is cooled down, stirs lower crystallization, filter, washing, gained filter cake is iminodiacetic acid
Crystal, crystalline mother solution recycled is in step (2).
2. according to the method described in claim 1, wherein, the gypsum by-product that iminodiacetic acid calcium crude product is acidified with sulfuric acid
Object, which is suspended in, to be passed through the ammonium hydroxide that carbon dioxide and alkaline hydrolysis workshop section generate and is converted in the ammonium hydroxide of by-product, after reaction terminates, mistake
Filter, washing, obtained solid is calcium carbonate；Filtrate cools down or condensing crystallizing isolates ammonium sulfate, and mother liquor continues to apply mechanically；The stone of generation
Cream or the calcium carbonate of the generation further converted-ammonium sulfate reaction mixture can not also detach, directly as composite fertilizer material.
3. according to the method described in claim 1, wherein, in step (1), iminodiacetonitrile or aminoacetonitriles and calcium oxide
Mass ratio be 1:0.1-1.0, reaction temperature are 50-90 DEG C；Reaction solution deamination temperature is controlled at 70-105 DEG C.
4. according to claim 1-3 any one of them methods, wherein in step (1), lime is digested with clear water, Huo Zheyong
Alkaline hydrolysis mother liquor digestion containing sodium sulphate, the aqueous solution of potassium sulfate or last consignment of.
5. according to claim 1-3 any one of them methods, wherein in step (2), sulfuric acid total acid content and iminodiacetic acid (salt)
The molar ratio of iminodiacetic acid in sour calcium crude product is 1-3：1, acidification terminal pH is 2, and the temperature of acidification is 50-105 DEG C, acid
The change time is 0.5h-5h.
6. according to claim 1-3 any one of them methods, wherein in step (2), the sulfuric acid amount that is added in gypsum wash water
It is advisable with the desired amount of 30%-50% of next group acidification reaction, wash temperature is controlled at 60 DEG C or more.
7. according to the method described in claim 2, wherein, reaction temperature is 30-70 DEG C, reaction time 0.5-5h.
8. according to the method described in claim 1, the material after alkaline hydrolysis deamination can be directly acidified without isolation, indissoluble is isolated
After property inorganic calcium salt, amino acid products are crystallized out, mother liquid recycle.
9. according to the method described in claim 1, isolating the terminal of the acidification of the filtrate tune acid after iminodiacetic acid calcium solid
For the isoelectric point of orresponding amino acid.
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| CN111100022A (en) * | 2019-10-30 | 2020-05-05 | 石家庄市栾城区华英工贸有限责任公司 | Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid |
| CN113563215B (en) * | 2021-07-30 | 2024-02-02 | 上海蓝科石化环保科技股份有限公司 | Glycine production process |
| CN116462599A (en) * | 2023-04-14 | 2023-07-21 | 天宝动物营养科技股份有限公司 | Co-production method of glycine and iminodiacetic acid |
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