CN105985251A - Clean production process for amino acids such as iminodiacetic acid - Google Patents
Clean production process for amino acids such as iminodiacetic acid Download PDFInfo
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Abstract
The invention relates to a clean production method for amino acids such as iminodiacetic acid. The method comprises the steps: carrying out alkaline hydrolysis on amino-nitrile by adopting cheap lime cream, and carrying out deamination, so as to obtain an iminodiacetic acid calcium salt crude product; suspending the obtained iminodiacetic acid calcium salt crude product into water or mother liquor, adding sulfuric acid or other inorganic acid into the water or mother liquor for acidification, and filtering out an inorganic calcium salt filter cake with low water solubility; and subjecting the filter liquor to cooling and crystallization, carrying out separation so as to obtain iminodiacetic acid solids, and applying the crystallization mother liquor to an acidification reaction of next batch mechanically. During the acidification by the sulfuric acid, gypsum can be converted into calcium carbonate and ammonium sulfate by further using a byproduct, i.e., ammonia water of an alkaline hydrolysis process and carbon dioxide in flue gas, so as to directly generate compound fertilizers; the calcium carbonate can also be separated, and ammonium sulfate crystals can also be concentrated; and the calcium carbonate can be sold as a byproduct or be subjected to heated decomposition so as to obtain a quicklime raw material which can be applied mechanically. According to the novel process, the complete utilization of resources can be realized, the reaction selectivity is higher, the production of colored byproducts is reduced, and a concentrating process for removing waste salts such as sodium sulfate and sodium chloride and a wastewater treatment link are avoided; and due to concentration, the use level of a decolorant can be greatly lowered, the energy saving and consumption lowering effects are remarkable, and the production cost is reduced remarkably.
Description
Technical field
The present invention relates to the process for cleanly preparing of the amino acidses such as iminodiacetic acid, belong to pesticide, chemical fertilizer and technical field of fine.
Background technology
Iminodiacetic acid, CAS 142-73-4, calls diglycinee, N-(carboxymethyl) glycine, ammonia oxalic acid, is called for short IDA.Iminodiacetic acid is mainly used as the intermediate of the pesticide such as synthesizing glyphosate, also is used as releasing phosphorus organic economic benefits and social benefits fertilizer, the raw material of ion exchange resin and rubber, plating, food additive etc. simultaneously.
Iminodiacetic acid has following several synthesis routes:
1, chloroactic acid method monoxone and ammonia or sodium hydroxide react production sodium chloroacetate, react generation hydrazine again with hydrazine hydrate and embrace oxalic acid, then it is acidified with hydrochloric acid again under sodium nitrite effect, generate iminodiacetic acid hydrochlorid, stand crystallization, sucking filtration, pickling, it is dissolved in hot water, adds sodium hydroxide solution and be neutralized, i.e. generate iminodiacetic acid.This method yield is low, and wastewater flow rate is big, complex steps, and the cost of raw material is high, is eliminated.
2, diethanolamine method diethanolamine method is the synthesis technique of the exploitation nineties in the world, with diethanolamine as primary raw material, in the presence of Cu-Ni alloy catalyst and sodium hydroxide, by high temperature (170 DEG C), (0.8 Mpa) with pressure deamination, generate iminodiacetic acid sodium, then be acidified synthesis of iminodiacetic acid.This method raw material diethanolamine is affected very big by crude oil price, and the brine waste of high concentration is difficult to process, and this technique is replaced by hydrocyanic acid method the most substantially.
3, this method of hydrocyanic acid method is current main flow production method both domestic and external.United States Patent (USP) US5,187,301 report and prepare Iminodiacetonitrile 1,1'-Imidodiacetonitrile with hydroxyacetonitrile, and Chinese patent CN1609112A reports and uses iminodiacetic acid disodium salt synthesis of iminodiacetic acid.The Iminodiacetonitrile 1,1'-Imidodiacetonitrile intermediate of hydrocyanic acid synthesis, with sodium hydroxide hydrolysis, acidifying, decolours, crystallizes, isolated iminodiacetic acid.There is alkaline hydrolysis yield losses and be easily generated coloring matter problem in the method, diacid yield only has about 90%, and the diacid waste water of a large amount of saliferous takes to concentrate desalination, the method for evaporation condensate biochemical treatment again, and energy consumption is high, and the poor quality of salt utilizes difficulty.Although the method for the Acid hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile synthesis of iminodiacetic acid of our exploitation decreases the use of by-product and sodium hydroxide, avoid production waste water, obtained valuable ammonium chloride, but it is complicated to there is subtractive process, solid-liquid separation often, invests bigger weak point.Therefore the aminoacid process for cleanly preparing that technique is simple, small investment, production cost are low is explored the most valuable.
Summary of the invention
It is an object of the invention to provide a kind of amino nitrile lime cream alkaline hydrolysis and prepare the process for cleanly preparing of the amino acids such as iminodiacetic acid, glycine.
We find under study for action, and amino nitrile uses to exist in sodium hydroxide alkali solution preocess and decomposes and aggregation problem, affects yield and product appearance.Its reason is owing to sodium hydroxide solution alkalescence is too strong, also cannot effectively suppress its decomposition raw material generation hydroxyacetic acid and glycine and formaldehyde and hydrocyanic acid polymerization to generate the side reaction of coloring matter even if controlling temperature.
The invention provides a kind of employing alkalescence and the calcium hydroxide that dissolubility is less than sodium hydroxide solution, cost is only sodium hydroxide about 1/5th substitutes sodium hydroxide and Iminodiacetonitrile 1,1'-Imidodiacetonitrile is carried out alkaline hydrolysis, the iminodiacetic acid calcium that water solublity is less can be obtained, can carry out separating or it is acidified by the mineral acid such as direct sulphuric acid, isolate the inorganic calcium salt filter cake that water solublity is low, the method that cooling crystallize obtains iminodiacetic acid.
Specifically, the present invention provides the method that the aminoacid cleanings such as a kind of iminodiacetic acid produce, and the method comprises the following steps:
(1) in lime cream, imido-diacetonitrile and/or the product of aminoacetonitriles, raw material or mother solution are added, after reacting 0.5-3 hour, deamination to control deamination terminal be 8-9 containing ammonia vapor pH, through filtering, washing, isolate iminodiacetic acid calcium crude product filter cake, alkaline hydrolysis mother solution and wash water as quick lime use water recycled or direct acid adjustment acidizing crystal；
(2) the iminodiacetic acid calcium crude product filter cake of gained in step (1) is added dispersed with stirring in the crystalline mother solution of water or iminodiacetic acid, add sulphuric acid or other is mineral acid acidified, filter out the inorganic calcium salt filter cake that water solublity is little, washing filter cake, washing liquid merges for next group diluting concentrated sulfuric acid or the material of other mineral acid, and filtrate is imido-oxalic acid solution；
(3) by the filtrate cooling of gained in step (2), the lower crystallize of stirring, to filter, washing, gained filter cake is iminodiacetic acid crystals, and crystalline mother solution recycled is in step (2).
Method the most according to claim 1, wherein,
The iminodiacetic acid calcium crude product sulphuric acid gypsum byproduct that obtains of acidifying is suspended in the ammonia of by-product and is passed through carbon dioxide and ammonia that alkaline hydrolysis workshop section produces converts, and after reaction terminates, filters, and washing, gained solid is calcium carbonate；Filtrate is lowered the temperature or concentrates crystallizable ammonium sulfate of isolating, and mother solution continues to apply mechanically；Calcium carbonate-ammonium sulfate the reactant mixture of the Gypsum Fibrosum generated or the generation converted further also can not separate, directly as composite fertilizer material.
Method the most according to claim 1, wherein, in step (1), the mass ratio of Iminodiacetonitrile 1,1'-Imidodiacetonitrile or aminoacetonitriles and calcium oxide is 1:0.1-1.0, and reaction temperature is 50-90 DEG C；Reactant liquor deamination temperature controls at 70-105 DEG C.
Method the most according to claim 1, wherein, in step (1), Calx can digest with clear water, or digests with the alkaline hydrolysis mother solution containing sodium sulfate, the aqueous solution of potassium sulfate or last consignment of.
5. according to the method described in any one of claim 1-4, wherein, in step (2), the total acid content of sulphuric acid or other mineral acid is 0.5-3:1 with the mol ratio of the iminodiacetic acid in iminodiacetic acid calcium crude product, acidifying terminal pH is 2, the temperature of acidifying is 50-105 DEG C, and acidificatoin time is 0.5 h-5 h.6., according to the method described in any one of claim 1-5, wherein, in step (2), the sulfuric acid amount added in Gypsum Fibrosum wash water is advisable with the desired amount of 30%-50% of next group acidification reaction, and wash temperature controls more than 60 DEG C.
Method the most according to claim 2, wherein, reaction temperature is 30-70 DEG C, and the response time is 0.5-5h.
Method the most according to claim 1, the material after alkaline hydrolysis deamination can the most directly be acidified, and after isolating slightly solubility inorganic calcium salt, crystallizes out amino acid products, mother liquid recycle.
Method the most according to claim 1, the terminal isolating the acidifying of the filtrate acid adjustment after iminodiacetic acid calcium solid is corresponding amino acid whose isoelectric point, IP.
Preparing as a example by iminodiacetic acid by Iminodiacetonitrile 1,1'-Imidodiacetonitrile below, the present invention is described in detail.
In step (1), the reactive chemistry formula using calcium hydroxide alkaline hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile is as follows:
During described alkaline hydrolysis, the composition of alkaline hydrolysis product is had a direct impact by the addition sequence of raw material, reaction temperature etc., and how optimizing reaction condition is the key point realizing alkaline hydrolysis.
The temperature needed during the reaction that the heat energy utilizing quick lime and water to react generation calcium hydroxide releasing can make whole system temperature arrive 50-60 DEG C, then input Iminodiacetonitrile 1,1'-Imidodiacetonitrile by several times, alkaline hydrolysis 0.5-3 h can make the Iminodiacetonitrile 1,1'-Imidodiacetonitrile in solution react completely.If the method according to other patents (publication number: CN101619077A), substep puts into Calx and Iminodiacetonitrile 1,1'-Imidodiacetonitrile, the impurity content such as nitrilotriacetic acid and glycine in product can be caused significantly to raise, wherein: the mass fraction of nitrilotriacetic acid is increased to 3.2% by not detecting of present invention process, and the mass fraction of glycine is increased to 0.09% by not detecting of present invention process.The common-ion effects such as this result shows, substep puts into Calx and Iminodiacetonitrile 1,1'-Imidodiacetonitrile, strong by reactant liquor alkalescence, calcium content is high are affected, and what Calx and water reacted is suppressed, and causes the alkaline hydrolysis time partially to grow (4-6 h), and by-product increases.Follow-up study finds, if the ammonia that in reactant liquor, remaining is a small amount of, deamination terminal point control at 8-9 at the steam pH containing ammonia, can make impurity nitrilotriacetic acid calcium calcium glycine be dissolved in mother solution, and the iminodiacetic acid calcium of the overwhelming majority separates out in solid form；If the method (publication number: CN101619077A) according to other patents, can be as deamination terminal using steam condensate (SC) weakly acidic pH, the mass fraction of nitrilotriacetic acid in product can be caused to be increased to 0.7% by not detecting of present invention process, and the mass fraction of glycine is increased to 0.09% by not detecting of present invention process.This result shows, deamination terminal point control at 8-9, can avoid nitrilotriacetic acid calcium and calcium glycine impurity to be together precipitated out with iminodiacetic acid calcium at the steam pH containing ammonia, is conducive to next step mother liquid recycle.
We have found that the existence containing sulfate radical material such as sodium sulfate, potassium sulfate in lime cream, alkaline hydrolysis and the deamination speed of Iminodiacetonitrile 1,1'-Imidodiacetonitrile can be promoted.
Further investigation revealed that the solubility with temperature change of iminodiacetic acid calcium is little, heat filtering can be carried out, it is not necessary to refilter after cooling.
For step (2), it has been found that the total acid content of the sulphuric acid of addition or other mineral acids can control 0.5-3:1 with the mol ratio of the iminodiacetic acid in iminodiacetic acid calcium crude product.When using sulphuric acid acidifying, the sulphuric acid heat of hydration and reaction heat can go out part water vapour with evaporation and concentration, it is simple to temperature regulation and water balance regulate, and acidifying 0.5-5 h, can make all of iminodiacetic acid calcium be fully converted to iminodiacetic acid at this temperature.Concrete reactive chemistry formula is as follows:
Filter the iminodiacetic acid being entrained with about 20% in gained Gypsum Fibrosum crude product, for avoiding with a large amount of hot wash Gypsum Fibrosum, increase and concentrate load, affect water balance.Can use at wash water or apply mechanically in wash water, adding the hot acid rinsing Gypsum Fibrosum of the mineral acid of next group reaction consumption 30%-50%, the washing liquid of separation adds remaining mineral acid for next group acidification reaction.Wash temperature controls more than 50 DEG C, on the one hand can improve iminodiacetic acid dissolubility in water, and Gypsum Fibrosum and sulfuric acid reaction on the other hand can be avoided to generate calcium bisulfate precipitation when using sulphuric acid acidifying.
For step (3), research finds that the dissolubility of iminodiacetic acid has the characteristic reduced with the reduction of temperature, such as: when 20 DEG C, its dissolubility in water is 2.6 g, is 9.73 g when 50 DEG C, is 23.8 g when 80 DEG C, is 50 g when 100 DEG C.Situation about can apply mechanically in view of energy-conservation and mother solution, we have selected acidifying at boiling temperature and obtain iminodiacetic acid～gypsum system heat filtering, hot filtrate cooling is water-cooled to less than 50 DEG C, and the most at least stirred crystallization 2 more than h, it is easy to filter with abundant crystallize, by filtering, washing can obtain iminodiacetic acid crystals.
Gained crystallization filtrate can be applied mechanically and next group acidification reaction.Activated carbon decolorizing is the most deeply can use to be continuing with if filtrate applies mechanically color after repeatedly.
Concentrated sulphuric acid and the mixing of hydrochloric acid that the method (CN101619077A) of other patents is taked are acidified so that iminodiacetic acid is with the method for hydrochloride form Yu Separation of gypsum.Not only need a large amount of concentrated mother liquor, frequently decolour, the glycine contained in iminodiacetic acid hydrochlorid solution and nitrilotriacetic acid, can cause the decline of PMIDA yield and quality, and lower mother solution apply mechanically number of times.
The present invention uses alternating temperature crystallize and mother liquid recycle scheme, avoids a large amount of concentrated mother liquor compared with the prior art, substantially avoided decolouring, simplify processing step, can reduce investment outlay, energy consumption can be greatly reduced, significantly reduce production cost, it is achieved cleaning produces..
Due to during Iminodiacetonitrile 1,1'-Imidodiacetonitrile alkaline hydrolysis can a large amount of ammonia of by-product, this part ammonia is capable of circulation as above or the raw material of other products.With the Gypsum Fibrosum of sulphuric acid acidifying iminodiacetic acid calcium by-product as cement, plasterboard raw material, it is also possible to nearby for salt-soda soil or acid soil improvement.In order to solve the outlet of by-product ammonia and store transportation problem, for a large amount of acid soil improvements and the needs of reduction of discharging, calcium carbonate and ammonium sulfate can be converted into as composite fertilizer material.For this, we have developed a kind of ammonia and Gypsum Fibrosum utilizing and producing iminodiacetic acid byproduct in process, produce calcium carbonate, ammonium sulfate and the method for calcium carbonate-ammonium sulfate compound fertilizer: the Gypsum Fibrosum crude product after sulfuric acid scrubbing in step (2) is added suitable quantity of water stirring, it is passed through rich carbonated flue gas and the ammonia of alkaline hydrolysis workshop section generation, 45-55 DEG C of reaction 2 h, filter, washing, obtaining calcium carbonate solid, being dried can be as commodity.Filtrate concentrates or cooling may separate out ammonia sulfate crystal, and mother solution continues to apply mechanically；Reactant mixture feed liquid also can not separate, and produces calcium carbonate-ammonium sulfate compound fertilizer.
In sum, new technology achieves lime cream quick alkaline hydrolysis height yield and prepares the target of iminodiacetic acid calcium, during our the most ingenious hydration heat that make use of Calx, sulphuric acid, and the reaction heat discharged in sulphuric acid acidization carries out system and rises gentleness concentration, energy consumption is greatly reduced, pass through by-product gypsum, it is to avoid mother liquor concentrations and a desalination difficult problem；By applying mechanically and alternating temperature crystallize strategy, greatly reducing iminodiacetic acid crystallization energy consumption, mother solution can recover system again, again avoiding the concentration power consumption in traditional handicraft and diacid loss；The Gypsum Fibrosum of by-product can be as side-product direct marketing；The ammonia that can also utilize carbon dioxide more than needed and alkaline hydrolysis workshop section by-product is further converted to raw material or fertilizer.
Therefore, new technology fundamentally overcomes the deficiency of existing technique, has got rid of and has concentrated the link of desalination, decreased activated carbon decolorizing number of times, saved substantial amounts of heat energy and cold energy, has improve product yield, inhibit by-product to generate, reach the notable energy-saving and cost-reducing and target of cleaning production.
Detailed description of the invention
Embodiment
1
Lime cream hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile prepares iminodiacetic acid calcium
Calx (31.4 g, 98%, 0. 55 mol), stirring reaction 15 min are put in water (200 g).Keep solution temperature at about 50 DEG C, add Iminodiacetonitrile 1,1'-Imidodiacetonitrile (50 g, 95%, 0.5 mol) by several times, finish about half an hour.Stirring 0.5-1 h at 50-55 DEG C, be warming up to about 90-100 DEG C, reduce pressure deamination, and moisturizing in good time, when the steam pH steamed is at 8-9, stops deamination.Filtering solution, washing.
Test iminodiacetic acid calcium crude product (113 g, imido-oxalic acid: 58 g,1Other impurity are had no on H-NMR), filtrate merges washing liquid (imido-oxalic acid: 5.2 g), and iminodiacetic acid calcium total recovery is 95.0%.
Embodiment
2
Lime cream hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile prepares iminodiacetic acid calcium, mother liquid recycle
In water (60 g), put into Calx (31.4 g, 98%, 0. 55 mol), stirring reaction 15 min, add the mother solution after the separation calcium salt of last batch.Keep solution temperature at about 50 DEG C, add Iminodiacetonitrile 1,1'-Imidodiacetonitrile (50 g, 95%, 0.5 mol) by several times, finish about half an hour.Stirring 0.5-1 h at 50-55 DEG C, be warming up to about 90-100 DEG C, reduce pressure deamination, and moisturizing in good time, when the steam pH steamed is at 8-9, stops deamination.Filtering out iminodiacetic acid calcium, washing, wash water merges mother liquid recycle and reacts in next group.
Experimental result is expressed as, and in 7 batch reaction iminodiacetic acid calcium crude products, iminodiacetic acid total recovery is 93.10%, and the IDA in final mother solution folds rate 2.26%, and 7 batch reaction iminodiacetic acid total recoverys are 95.50%.
Embodiment
3
Patent (publication number:
CN101619077A
) method prepares iminodiacetic acid calcium
Add water 872 mL in the reactor, is evacuated to 0.1 Mpa, is warming up to 45-50 DEG C, by Calx, (70%, 143 g) (95%, 151 g) are uniformly added in water several times with Iminodiacetonitrile 1,1'-Imidodiacetonitrile, every 5 min add 1 time, and 3 h finish, insulation reaction 1 h, it is warming up to 75 DEG C again, insulation reaction 2 h, then it is warming up to 100 DEG C, insulation reaction, terminates reaction, cooling when being 7 to steam pH, filter, collect filtrate and filter cake respectively.
Test iminodiacetic acid calcium crude product (117 g, imido-oxalic acid: 58.8 g, impurity: nitrilotriacetic acid: 3.8 g, glycine: 0.1 g), filtrate merge washing liquid (imido-oxalic acid: 3.53 g), iminodiacetic acid total recovery is 93.8%.
Comparing embodiment 1, the method prepares iminodiacetic acid calcium, and the response time is long, containing the impurity such as nitrilotriacetic acid, glycine in product.
Embodiment
4
Lime cream hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile, deamination terminal point control is at steam
pH = 7
Calx (31.4 g, 98%, 0. 55 mol), stirring reaction 15 min are put in water (200 g).Keep solution temperature at about 50 DEG C, add Iminodiacetonitrile 1,1'-Imidodiacetonitrile (50 g, 95%, 0.5 mol) by several times, finish about half an hour.Stirring 0.5-1 h at 50-55 DEG C, be warming up to about 90-100 DEG C, reduce pressure deamination, and moisturizing in good time, when steam pH=7 steamed, stops deamination.Filtering solution, washing.
Test to obtain iminodiacetic acid calcium crude product (118 g, imido-oxalic acid: 60 g, nitrilotriacetic acid 0.8 g, glycine: 0.1 g), filtrate merges washing liquid (imido-oxalic acid: 3.0 g, nitrilotriacetic acid 0.8 g, glycine: 0.5 g), iminodiacetic acid total recovery is 95.0%.
Compare embodiment 1, if deamination terminal point control is in pH=7 of steam, the impurity such as nitrilotriacetic acid can be caused together to separate out with iminodiacetic acid calcium.
Embodiment
5
Iminodiacetic acid calcium dissolubility at different temperatures
We have detected under different temperatures, iminodiacetic acid calcium dissolubility in water, and result shows, the change of solubility with temperature is little, stable at about 1 g.
Embodiment
6
Iminodiacetic acid dissolubility at different temperatures
We have detected under different temperatures, iminodiacetic acid dissolubility in water, and result shows, the rising of solubility with temperature and raise.
Embodiment
7
Sulphuric acid acidifying iminodiacetic acid calcium
By iminodiacetic acid calcium crude product, (35 g, imido-oxalic acid 20 g) is added to the water (100 g), and (98%, 15.1 g), keeps 95-100 DEG C of reaction 1h, concentrates, and before keeping filtering, cumulative volume is in about 125mL, filtered while hot to drip sulphuric acid under stirring.Detect filtrate and the filter cake of gained respectively.
Experimental result shows, containing iminodiacetic acid 14.5 g in filtrate, yield is 72.5%；Filter cake is carried secretly iminodiacetic acid 5.5 g；Overall yield of reaction is more than 99%.
Embodiment
8
Dilution heat of sulfuric acid washing Gypsum Fibrosum crude product
By sulphuric acid, (98%, 5 g) add in wash water (25 g), are warming up to 70 DEG C, and the filter cake in washing embodiment 7 filters, and filter cake clear water (5 g) washs.Imido-oxalic acid 5.4 g in filtrate；Weight 23.5 g after filtration cakes torrefaction, with CaSO4· 0.5 H2O meter productivity is more than 99%, and the iminodiacetic acid carried secretly is less than 0.05 g.
Embodiment
9
Iminodiacetic acid (salt) acid solution cooling crystallize prepares iminodiacetic acid
By gained filtrate in embodiment 7, (170 g, g), stirring decline warms to room temperature imido-oxalic acid 14.5, and at room temperature crystallize 2 h, filters, and washing, (157 g, imido-oxalic acid 3.5 is g) for wash water merging filtrate.Filtration cakes torrefaction, smashing weighs obtains iminodiacetic acid 11.8 g, content 99.5%.
Embodiment
10
Sulphuric acid acidifying iminodiacetic acid calcium, after filtrate crystallize, recycled
Iminodiacetic acid calcium crude product (35 g, imido-oxalic acid 20g) is added to the water (100 g), under stirring, drips sulphuric acid (98%, 15.1 g), keeps 95-100 DEG C of reaction 1 h, concentrates excessive moisture, before keeping filtering, cumulative volume is in 125-150 about mL, filtered while hot.Filtrate stirring decline warms to room temperature, and at room temperature crystallize 2 h filters, washs 2 times with water (15 g), and 1 wash water is used for washing Gypsum Fibrosum crude product, and 2 wash waters are as 1 wash water of next group product.Product drying, smashing is weighed.Crystalline mother solution set is for next group acidification reaction.
By sulphuric acid, (98%, 5 g) add in product wash water and clear water (20-25 g), are warming up to 70 DEG C, wash filter cake, filter, and filter cake clear water (5 g) washs 2 times, and 1 time wash water integrates with cleaning mixture, and 2 wash waters are as 1 wash water of next group Gypsum Fibrosum.Merge cleaning mixture and clear water, add remaining sulphuric acid, for the acidifying of next group reaction.Last batch of Gypsum Fibrosum uses a large amount of hot washes, and washing liquid integrates with crystalline mother solution.
(140 g, imido-oxalic acid: 10.89 g) add activated carbon (0.6 g), are warming up to 80 DEG C, stir 1 h at this temperature last iminodiacetic acid crystalline mother solution, and cooling is filtered, washing.Crystalline mother solution color can be light brown by black transitions.Concentrate most moisture, be dried gained solid, obtain iminodiacetic acid (11.5 g, purity 95.1%).Activated carbon dilute hydrochloric acid solution washs repeatedly, imido-oxalic acid 0.21 g in detection washing liquid.
Experimental result shows, 7 batches of acidification reaction iminodiacetic acid product yields 97.4%, the in conjunction with the embodiments results of 2, hydrolyzed through Calx by Iminodiacetonitrile 1,1'-Imidodiacetonitrile, sulphuric acid is acidified, and the total recovery being prepared into iminodiacetic acid is: 90.7%, and the total recovery of half-H 2 O calcium sulphate is more than 99%.
Embodiment
11
Gypsum Fibrosum crude product prepares ammonium sulfate and calcium carbonate
By gained Gypsum Fibrosum crude product in embodiment 8, (30 g g) mix with water (30 g) containing half-H 2 O calcium sulphate 23.5, are warming up to 45-55 DEG C, are passed through ammonia and carbon dioxide to solution under stirring.After reaction 1.5-2 h, gained solution, through filtering, concentrates, obtains ammonia sulfate crystal (18.2 g), productivity 85.1%；After filtration cakes torrefaction, obtain calcium carbonate powder (15.3 g, calcium carbonate 13.8 g, mean diameter 7.8 μm)；Solution also can not separate, direct concentrate drying, and (36 g, liquid containing ammonium sulfate 18.2 g, calcium carbonate 13.8 is g) can to obtain ammonium sulfate-compound of calcium carbonate.
Embodiment
12
Calx
+
Sodium sulfate hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile prepares iminodiacetic acid calcium
In water (200g), put into Calx (31.4g, 98%, 0.55 mol) and anhydrous sodium sulfate (85.2g, 99%, 0.65mol), stir 15 min.Maintain the temperature at about 50 DEG C, add Iminodiacetonitrile 1,1'-Imidodiacetonitrile (50g, 95%, 0.5 mol) by several times, finish about half an hour.50-55 DEG C of stirring 0.5-1 h, is warmed up to about 90-100 DEG C, and decompression deamination 1-2 hour, when steaming steam pH at 8-9, stops deamination.Filtering solution, washing.
Experiment obtain iminodiacetic acid calcium crude product (100.9g, imido-oxalic acid: 48.1g,1Other impurity are had no on H NMR), filtrate merges washing liquid (imido-oxalic acid: 16.4g), and the total recovery of iminodiacetic acid is 96.9%.
Embodiment
13
Calx
+
A small amount of sodium sulfate hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile prepares iminodiacetic acid calcium
In water (200g), put into Calx (31.4g, 98%, 0.55 mol) and anhydrous sodium sulfate (7.2g, 99%, 0.055mol), stir 15 min.Maintain the temperature at about 50 DEG C, add Iminodiacetonitrile 1,1'-Imidodiacetonitrile (50g, 95%, 0.5 mol) by several times, finish about half an hour.50-55 DEG C of stirring 0.5-1 h, is warmed up to about 90-100 DEG C, and decompression deamination 1-2 hour, when steaming steam pH at 8-9, stops deamination.Filtering solution, washing.
Experiment obtain iminodiacetic acid calcium crude product (86.9g, imido-oxalic acid 47.8g,1Other impurity are had no on H NMR), filtrate merges washing liquid (imido-oxalic acid 15.8g), and the total recovery of iminodiacetic acid is 95.7%.
Embodiment
14
Lime cream hydrolysis Iminodiacetonitrile 1,1'-Imidodiacetonitrile reaction mixture prepares iminodiacetic acid calcium
It is 9.9g to the reaction mixture 50g(Iminodiacetonitrile 1,1'-Imidodiacetonitrile of Iminodiacetonitrile 1,1'-Imidodiacetonitrile, aminoacetonitriles is 0.7g, ammonia three acetonitrile is 0.5g, and hydroxyacetonitrile is 0.8g, and ammonium sulfate is 6.2g) middle input 13.6g Calx, maintain the temperature at about 50-55 DEG C to stir 2 hours, being warmed up to about 90-100 DEG C, reduce pressure deamination, and moisturizing in good time, when normal steam pH is at 8-9, stop deamination.Filtering solution, washs solid.
Experiment obtain iminodiacetic acid calcium crude product (24.3g, imido-oxalic acid 11.7-g,1Other impurity are had no on H NMR), filtrate merges washing liquid (119.7-g, imido-oxalic acid 1.6-g), and the total recovery of iminodiacetic acid is 95.8%.
Embodiment
15
Calx
+
Sodium sulfate alkaline hydrolysis prepares glycine
To 40 DEG C of ammonia 83.5g, 25.0%, 1.23mol) middle addition hydroxyacetonitrile (50.0g, 40.1%, 0.35mol).At 50 DEG C, stirring reaction 1h, adds Calx (9.8g, 98%, 0.175mol) and sodium sulfate (12.5g by this ammonification drop, 99.0%, 0.09mol) in mixed aqueous solution, 70 DEG C of alkaline hydrolysis 2h, it is warming up to about 100 DEG C decompression deaminations, as the steam pH=8-9 steamed, stops deamination.Filter, washing, merging filtrate and wash water.
Filtrate merges washing liquid (111.8g, imido-oxalic acid 4.4g, glycine 19.4g, nitrilotriacetic acid 0.5g, hydroxyacetic acid 0.9g), filtering residue (13.3g, imido-oxalic acid 0.2g, glycine 0.1g, nitrilotriacetic acid and hydroxyacetic acid nuclear-magnetism do not detect).
Claims (9)
1. the aminoacid process for cleanly preparing such as iminodiacetic acid, the method comprises the following steps:
(1) in lime cream, imido-diacetonitrile and/or the product of aminoacetonitriles, raw material or mother solution are added, after reacting 0.5-3 hour, deamination to control deamination terminal be 8-9 containing ammonia vapor pH, through filtering, washing, isolate iminodiacetic acid calcium crude product filter cake, alkaline hydrolysis mother solution and wash water as quick lime use water recycled or direct acid adjustment acidizing crystal；
(2) the iminodiacetic acid calcium crude product filter cake of gained in step (1) is added dispersed with stirring in the crystalline mother solution of water or iminodiacetic acid, add sulphuric acid or other is mineral acid acidified, filter out the inorganic calcium salt filter cake that water solublity is little, washing filter cake, washing liquid merges for next group diluting concentrated sulfuric acid or the material of other mineral acid, and filtrate is imido-oxalic acid solution；
(3) by the filtrate cooling of gained in step (2), the lower crystallize of stirring, to filter, washing, gained filter cake is iminodiacetic acid crystals, and crystalline mother solution recycled is in step (2).
Method the most according to claim 1, wherein, the iminodiacetic acid calcium crude product sulphuric acid gypsum byproduct that obtains of acidifying is suspended in the ammonia of by-product and is passed through carbon dioxide and ammonia that alkaline hydrolysis workshop section produces converts, after reaction terminates, filtering, washing, gained solid is calcium carbonate；Filtrate is lowered the temperature or concentrates crystallizable ammonium sulfate of isolating, and mother solution continues to apply mechanically；Calcium carbonate-ammonium sulfate the reactant mixture of the Gypsum Fibrosum generated or the generation converted further also can not separate, directly as composite fertilizer material.
Method the most according to claim 1, wherein, in step (1), the mass ratio of Iminodiacetonitrile 1,1'-Imidodiacetonitrile or aminoacetonitriles and calcium oxide is 1:0.1-1.0, and reaction temperature is 50-90 DEG C；Reactant liquor deamination temperature controls at 70-105 DEG C.
4. according to the method described in any one of claim 1-3, wherein, in step (1), Calx can digest with clear water, or digests with the alkaline hydrolysis mother solution containing sodium sulfate, the aqueous solution of potassium sulfate or last consignment of.
5. according to the method described in any one of claim 1-4, wherein, in step (2), the total acid content of sulphuric acid or other mineral acid is 1-3:1 with the mol ratio of the iminodiacetic acid in iminodiacetic acid calcium crude product, acidifying terminal pH is 2, the temperature of acidifying is 50-105 DEG C, and acidificatoin time is 0.5 h-5
h。
6., according to the method described in any one of claim 1-5, wherein, in step (2), the sulfuric acid amount added in Gypsum Fibrosum wash water is advisable with the desired amount of 30%-50% of next group acidification reaction, and wash temperature controls more than 60 DEG C.
Method the most according to claim 2, wherein, reaction temperature is 30-70 DEG C, and the response time is 0.5-5h.
Method the most according to claim 1, the material after alkaline hydrolysis deamination can the most directly be acidified, and after isolating slightly solubility inorganic calcium salt, crystallizes out amino acid products, mother liquid recycle.
Method the most according to claim 1, the terminal isolating the acidifying of the filtrate acid adjustment after iminodiacetic acid calcium solid is corresponding amino acid whose isoelectric point, IP.
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| 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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