CN109369429B - Device and method for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid - Google Patents
Device and method for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid Download PDFInfo
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Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to a device and a method for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid. The device comprises an acid preparation device, an ammonia water preparation device, a reaction system, a decoloring system, a solid-liquid separation system I, an evaporative crystallization system and a solid-liquid separation system II which are connected in sequence. Wherein, a liquid outlet of the solid-liquid separation system II is connected with the decoloring system; a feed inlet of the reaction system is connected with an acid preparation device; an ammonia water feeding port is arranged on the solid-liquid separation system I. The invention also provides a method for preparing iminodiacetic acid by utilizing the device. The invention simplifies the production process, greatly improves the total yield of IDA and has better economic benefit; the method has the advantages of short process flow, less waste water and obvious environmental protection advantage, and can be used for large-scale production.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a device and a method for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid.
Background
Iminodiacetic acid (also known as diglycine or iminodiacetic acid, IDA for short) with the molecular formula NH (CH)2COOH)2The metal surface treatment agent is an important fine chemical product, has strong complexing effect, can form a chelate with various metal ions, has wide application in the aspects of pesticides, dyes, chemical engineering, water treatment, medicines, functional polymers, electrons and the like, and is an important raw material and an intermediate for pesticides, pharmacy, rubber, surfactants, complexing agents, food additives, electroplating industry, synthetic metal surface treatment agents, ion exchange resins thereof and the like.
The domestic industrial production method of iminodiacetic acid mainly has four methods: the domestic industrial production method of iminodiacetic acid mainly comprises four methods, namely iminodiacetonitrile base hydrolysis method, iminodiacetonitrile acid hydrolysis method, chloroacetic acid method and diethanolamine oxidation method. The chloroacetic acid method is characterized in that chloroacetic acid reacts with ammonia water and calcium hydroxide, then is acidified by hydrochloric acid to generate iminodiacetic acid hydrochloride, and the iminodiacetic acid hydrochloride is kept stand for crystallization, is subjected to suction filtration and acid cleaning, is dissolved in hot water, is added with sodium hydroxide solution to generate iminodiacetic acid, and is crystallized, separated and dried to obtain a product, wherein the method has the mature process, but has the defects of long flow, low product purity, high cost, serious three wastes and the like; the iminodiacetonitrile acid hydrolysis method is to hydrolyze iminodiacetonitrile and hydrochloric acid or sulfuric acid to directly obtain iminodiacetic acid and ammonium chloride or ammonium sulfate; the diethanolamine oxidation method and the iminodiacetonitrile alkali hydrolysis method both change the raw material into iminodiacetic acid disodium salt, then use hydrochloric acid or sulfuric acid for acidification to obtain the mixture of iminodiacetic acid and sodium chloride or sodium sulfate, and then separate to obtain iminodiacetic acid.
At present, iminodiacetonitrile is hydrolyzed by alkali and then is acidified, which is the most common preparation method of iminodiacetic acid, a common separation method is to acidify iminodiacetic acid disodium salt into iminodiacetic acid and corresponding inorganic salt by hydrochloric acid or sulfuric acid, the iminodiacetic acid and the corresponding inorganic salt are separated by utilizing the characteristic that the iminodiacetic acid has low solubility in water and the inorganic salt has high solubility in water, and mother liquor is continuously used; or the iminodiacetic acid disodium salt is hydrochlorinated into iminodiacetic acid monosodium salt and sodium chloride or sodium sulfate, the inorganic salt is firstly separated by utilizing the solubility characteristics of the iminodiacetic acid monosodium salt and the inorganic salt, and then the iminodiacetic acid is obtained by acidification separation and mother liquor is reused.
The iminodiacetonitrile mother liquor contains a large amount of iminodiacetonitrile, hydroxyl acetonitrile, aminoacetonitrile, sulfuric acid, ammonium bisulfate, ammonium sulfate and other organic polymers, and is generally treated as waste liquor by incineration due to complex components. However, the mother liquor has high salt content and water content, is difficult to burn, has very low combustion heat value, can generate a large amount of acid gas in the combustion process of the mother liquor to cause secondary pollution and corrosion of metal equipment, and organic polymers generated in the combustion process are easy to block an incinerator. Therefore, the existing method for treating the iminodiacetonitrile mother liquor has the defects of serious resource waste, high treatment difficulty, secondary pollution, no economic value and the like. In addition, impurities contained in the iminodiacetonitrile mother liquor are hydrolyzed and acidified to influence the yield of iminodiacetic acid and the recycling frequency of the mother liquor, and the generation amount of wastewater and the treatment difficulty are increased.
Chinese patent CN101391911A discloses a method for preparing an organic fertilizer by using waste liquid from aminonitrile production, which comprises the steps of adding a catalyst and a dispersing agent into the waste liquid from aminonitrile production to prepare a base fertilizer, then inoculating biological bacteria into the base fertilizer, fermenting for 7-15 days, hydrolyzing to obtain a raw material fertilizer, and preparing the raw material fertilizer into the organic fertilizer through the working procedures of nutrient blending, granulation, drying and the like. The method realizes the integral resource utilization of the cyanide-containing wastewater, but the waste liquid treatment time is too long, a large-scale composting site is needed, and the conversion and utilization value is low.
Chinese patent CN103483031A discloses a method for preparing amino acid compound by taking iminodiacetonitrile waste water as raw material. Taking iminodiacetonitrile waste water generated in the process of producing iminodiacetonitrile as a raw material, adding an auxiliary agent, stirring and polymerizing for 6-120 minutes at the temperature of 50-280 ℃, adding two composite catalysts after the polymerization is finished, carrying out amino acidification reaction for 10-150 minutes at the temperature of 50-200 ℃ to obtain a liquid amino acid composite, and drying the liquid to obtain a solid amino acid composite. The method has high energy consumption, and the obtained product has complex composition and limited application.
Chinese patent CN101503367A discloses a method for synthesizing nitrilotriacetic acid from residual liquid of iminodiacetonitrile produced by hydrocyanic acid method. The method specifically comprises the following steps: 1) adding alkali into the residual liquid of iminodiacetonitrile, hydrolyzing at 30-100 ℃, adding chloroacetic acid into hydrolysate, adjusting the pH value to 9-14 with alkali at 10-100 ℃, reacting for 0.5-10 hours, adding acid into the reaction liquid, and acidifying to separate out a crude product of nitrilotriacetic acid. 2) Suspending the crude product of nitrilotriacetic acid in water, adding alkali to neutralize and dissolve under stirring, decoloring by using activated carbon, removing the activated carbon, acidifying, filtering and drying to obtain a finished product of the nitrilotriacetic acid. The method has the disadvantages that a large amount of residual hydroxy acetonitrile in the mother liquor can not be effectively utilized, a large amount of alkali and acid are consumed, a large amount of inorganic salt is generated, the energy consumption is high, and the amount of waste water is increased.
The applicant produces about 2000 tons of various wastes from the production of iminodiacetonitrile, and the wastes are not only environmentally friendly but also have quality reduction after long-term storage, and are difficult to recycle. The iminodiacetonitrile feed liquid adopts falling film evaporation, and the raffinate after taking the crystal is burnt by a waste liquid incinerator, on one hand, the product recovery rate is low, the energy consumption is high, on the other hand, the environmental protection risk is caused, and the burning tail gas contains nitrogen and oxysulfide.
Therefore, the applicant solves the problem of overstocking of iminodiacetonitrile waste materials and the problem of environmental protection by developing the device of the invention, and effectively processes the iminodiacetonitrile production feed liquid to prepare the iminodiacetic acid with economic value.
Disclosure of Invention
In view of the above, the present invention aims to provide an apparatus and a method for preparing iminodiacetic acid from iminodiacetonitrile feed liquid, wherein the apparatus can effectively treat the iminodiacetonitrile feed liquid to prepare iminodiacetic acid with economic value, and has the advantages of short treatment process, less wastewater and reduced environmental risk.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the device for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid is characterized by comprising an acid preparation device (1), an ammonia water preparation device (2), a reaction system (3), a decoloring system (4), a solid-liquid separation system I (5), an evaporative crystallization system (6) and a solid-liquid separation system II (7) which are connected in sequence; a liquid outlet of the solid-liquid separation system II (7) is connected with the decoloring system (4); a feed inlet of the reaction system (3) is connected with an acid distributor (1); the solid-liquid separation system I (5) is connected with the ammonia water preparation device (2). The device adopts a full-flow intermittent mode to produce.
Preferably, the reaction equipment is made of glass lining or modified glass fiber reinforced plastic. The concentration of sulfuric acid used in the direct acid hydrolysis of iminodiacetonitrile feed liquid is higher, and the temperature is higher than 100 ℃, so that the traditional glass fiber reinforced plastic can not be used as the material of the reaction kettle.
Further, the condensed water obtained by the evaporative crystallization system is circulated to an acid preparation device to prepare a sulfuric acid solution and/or is circulated to an ammonia water preparation device to prepare ammonia water.
The condensed water of the evaporative crystallization system is fully utilized, the generation of waste water is reduced, and the production cost is reduced.
Further, concentrated mother liquor obtained by the solid-liquid separation system II enters a decoloring system for cyclic utilization, so that cyclic utilization of iminodiacetonitrile mother liquor is realized.
Further, the iminodiacetonitrile feed liquid is (1) prepared by reacting hydrocyanic acid, hexamethylenetetramine and formaldehyde as raw materials; (2) heating and disproportionating aminoacetonitrile; (3) reacting hydroxyl acetonitrile with aminoacetonitrile; (4) hydroxyl acetonitrile and ammonia are used as raw materials to react in one or more ways.
Furthermore, the iminodiacetonitrile feed liquid can also be derived from one or more of reaction liquid, crystallization mother liquid and concentrated mother liquid obtained by the reaction of the device.
The second purpose of the invention is to provide a method for preparing iminodiacetic acid by using iminodiacetonitrile feed liquid as a raw material by utilizing the device, which comprises the following steps:
1) feeding 65-75% sulfuric acid solution prepared by an acid preparation device into a reaction system through a feed inlet of the reaction system, continuously adding iminodiacetonitrile production liquid into the reaction system for hydrolysis, and transferring the iminodiacetonitrile production liquid into a decoloring system for decoloring to obtain a decoloring liquid;
2) adding ammonia water prepared by an ammonia water preparation device into a solid-liquid separation system I through an ammonia water feeding hole, transferring a decolorized liquid obtained by the decolorized system into the solid-liquid separation system I to participate in reaction, adjusting the pH value of a feed liquid to be 1.5-3, continuing introducing ammonia when the pH value is less than 1-3 in the process of adjusting the pH value, and adding sulfuric acid when the pH value is more than 1-3. Cooling and crystallizing after reaction, and separating by a solid-liquid separation system I to obtain iminodiacetic acid and crystallization mother liquor;
3) transferring the crystallization mother liquor obtained in the step 2) to an evaporation crystallization system, introducing ammonia, adjusting the pH value of the solution to 7-7.5 for evaporation crystallization, and separating by a solid-liquid separation system II to obtain ammonium sulfate and concentrated mother liquor.
The reaction process is as follows:
(2)NH4HSO4+NH3→(NH4)2SO4
4) and 3) feeding the concentrated mother liquor obtained from the solid-liquid separation system II into a decoloring system for cyclic application, and continuing to participate in the next reaction. The problem of cyclic utilization of the iminodiacetonitrile mother liquor is solved.
Further, the reaction temperature in the step 1) is 100-120 ℃, and the decoloring temperature is 70-90 ℃.
Further, activated carbon and/or hydrogen peroxide are/is added into the decoloring system in the step 1); the using amount of the active carbon is 1 to 10 percent of the weight of the iminodiacetic acid; the dosage of the hydrogen peroxide is 1 percent. Preferably, the amount of activated carbon is 6% by weight of iminodiacetic acid.
Further, water evaporated in the micro-boiling state at the reaction temperature of 100-120 ℃ in the step 1) is condensed and then circulated to a decoloring system.
Transferring the prepared sulfuric acid into a reaction system, adding the iminodiacetonitrile feed liquid into the reaction system under the condition of micro negative pressure, keeping the reaction temperature at 100-120 ℃ in a micro boiling state, and distilling water while feeding the iminodiacetonitrile feed liquid. The water evaporated after condensation is directly purified and crystallized. And preserving the heat for 4 hours at 105-120 ℃ after the feeding is finished.
Further, the conversion rate of the iminodiacetonitrile feed liquid in the step 1) is transferred to a decoloring system for processing after 90-97 percent.
Preferably, the conversion rate of the material liquid for producing the iminodiacetonitrile in the middle control step 1) is 95 to 97 percent.
Preferably, after the intermediate control is qualified, the temperature is reduced to 80 +/-5 ℃, activated carbon is added for decolorization treatment, and then purification and crystallization are carried out.
Further, washing and drying the iminodiacetic acid obtained by solid-liquid separation in the step 2) to obtain an iminodiacetic acid product, wherein the washing water is recycled.
Further, adding ammonia to adjust the pH value to 1.5-3 in the step 2); the reaction temperature is 60-80 ℃.
Further, the temperature for cooling and crystallizing in the step 2) is 10-40 ℃, and the crystallizing time is 0.5-4 h.
The invention also provides a method for preparing the ammonium sulfate mixture by using the device, which takes iminodiacetonitrile feed liquid as a raw material, adds water to carry out hydrolysis reaction with sulfuric acid, continuously reacts the hydrolysate with ammonia, and obtains the ammonium sulfate mixture through evaporation and crystallization, wherein the mixture contains ammonium sulfate and a small amount of iminodiacetic acid.
The invention has the beneficial effects that:
1) the device for preparing iminodiacetic acid by utilizing the iminodiacetonitrile feed liquid takes the iminodiacetonitrile feed liquid as a raw material, the production process is simplified, a plurality of working procedures of crystallization, concentration, secondary crystallization, mother liquid sedimentation, waste liquid incineration and the like of the original iminodiacetonitrile process are omitted, the generation of iminodiacetonitrile products with poor quality is avoided, the total yield of IDA is greatly improved, and the economic benefit is better.
2) The method effectively treats the iminodiacetonitrile feed liquid to prepare the iminodiacetic acid with economic value, has short process flow, less waste water and obvious environmental protection advantage, avoids using sodium hydroxide, reduces the production cost and the energy consumption, and can carry out large-scale production.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing iminodiacetic acid from iminodiacetonitrile feed solution according to the present invention.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The experimental methods of the preferred embodiments, which do not indicate specific conditions, are generally performed according to conventional conditions, and the examples are given for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1
Device for preparing iminodiacetic acid by utilizing iminodiacetonitrile production feed liquid
The device for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid is characterized by comprising an acid preparation device (1), an ammonia water preparation device (2), a reaction system (3), a decoloring system (4), a solid-liquid separation system I (5), an evaporative crystallization system (6) and a solid-liquid separation system II (7) which are connected in sequence; a liquid outlet of the solid-liquid separation system II (7) is connected with the decoloring system (4); a feed inlet of the reaction system (3) is connected with an acid distributor (1); the solid-liquid separation system I (5) is connected with the ammonia water preparation device (2). Circulating the condensed water obtained by the evaporative crystallization system to an acid preparation device to prepare a sulfuric acid solution; circulating the condensed water obtained by the evaporative crystallization system to an ammonia water preparation device to prepare ammonia water; and (3) feeding the concentrated mother liquor obtained by the solid-liquid separation system II into a decoloring kettle for recycling.
Example 2
Method for preparing iminodiacetic acid by using iminodiacetonitrile production feed liquid as raw material by utilizing device
The method for preparing iminodiacetic acid by using iminodiacetonitrile production feed liquid as raw material by utilizing the device comprises the following steps:
1) transferring a sulfuric acid solution prepared by an acid preparation device into a reaction device through a feed inlet of a reaction system, continuously adding an iminodiacetonitrile feed liquid into the reaction system for hydrolysis, reacting at 105-120 ℃, transferring the iminodiacetonitrile feed liquid into a decoloring system after the conversion rate of the iminodiacetonitrile feed liquid is 90-97%, adding activated carbon for decoloring, and decoloring at 70-90 ℃ to obtain a decoloring solution.
2) Adding ammonia water prepared by an ammonia water preparation device into a solid-liquid separation system I through an ammonia water feeding hole, transferring the obtained decolorized liquid into the ammonia water feeding hole for reaction, adjusting the pH value of the feed liquid to be 1.5-3, cooling and crystallizing at 25-35 ℃ for 0.5-4 h after the reaction at 60-80 ℃, and separating by the solid-liquid separation system I to obtain iminodiacetic acid and crystallized mother liquor; washing and drying the iminodiacetic acid to obtain an iminodiacetic acid product, and recycling washing water;
3) transferring the crystallization mother liquor obtained in the step 2) into an evaporation crystallization system, introducing gas ammonia, adjusting the pH value of the solution to be more than 7, carrying out evaporation crystallization, and carrying out n-type separation by a solid-liquid separation system to obtain ammonium sulfate; enabling concentrated mother liquor obtained by the solid-liquid separation system II to enter a decoloring system for cyclic application; the condensed water of the evaporative crystallization system is circulated to an acid preparation device to prepare a sulfuric acid solution and is circulated to an ammonia water preparation device to prepare ammonia water.
Example 3
Preparation of ammonium sulfate
Single batch experiment
1) Water and sulfuric acid are added into a reaction device to prepare a 75% sulfuric acid solution.
2) Heating to 110 ℃, slowly and continuously dripping iminodiacetonitrile feed liquid, controlling the reaction temperature to be 110 +/-5 ℃, and keeping the temperature at 110 ℃ for 2 hours after the charging is finished.
3) After the reaction is finished, 100ml of water, 100ml of ammonia water and activated carbon are added, and the temperature is kept for 1h (the temperature is controlled to be 80-90 ℃) and then the filtration is carried out.
4) After suction filtration, the pH value is adjusted to 2.0 by ammonia water (the temperature is controlled to be not more than 70 ℃), and the crystal is cooled.
5) And (4) carrying out suction filtration to obtain an IDA product, and reserving the residual filtrate as mother liquor for concentration and continuous application.
Concentrating
1) The mother liquor obtained by suction filtration is adjusted to pH 7.0 and heated for concentration.
2) The total volume of 1/3 is concentrated for the first time, and ammonium sulfate crystals are taken out when the solution is hot.
3) The mother liquor of the second time is concentrated to total volume 1/3, and ammonium sulfate crystals are taken out when the mother liquor is hot.
Single batch experimental data
Example 4
Production of iminodiacetic acid from iminodiacetonitrile reaction liquid or crystallization liquid
1. Single batch protocol
1) Water and sulfuric acid are added into a reaction device to prepare a 75% sulfuric acid solution.
2) Raising the temperature to 105 ℃, slowly adding the iminodiacetonitrile reaction solution, controlling the reaction temperature to be about 110 ℃, and performing micro-negative pressure water evaporation for more than 3 hours after the addition is finished.
3) Continuously adding the iminodiacetonitrile reaction solution, controlling the reaction temperature to be about 115 ℃, and adding sulfuric acid after the addition is finished.
4) After the sulfuric acid is added, adding iminodiacetonitrile reaction liquid, controlling the reaction temperature to be about 115 ℃, and performing micro-negative pressure water evaporation for more than 3 hours after the addition is finished.
5) Continuously adding the iminodiacetonitrile reaction solution, controlling the reaction temperature to be about 115 ℃, and adding sulfuric acid after the addition is finished.
6) After the sulfuric acid is added, adding iminodiacetonitrile reaction liquid, controlling the reaction temperature to be about 115 ℃, and performing micro-negative pressure water evaporation for more than 3 hours after the addition is finished. And (5) preserving the heat after the water evaporation is finished.
7) After the heat preservation is finished, the temperature is reduced to about 80 ℃, hydrogen peroxide is slowly added, and the heat preservation is carried out for 0.5h at the temperature of 80-90 ℃.
8) After the heat preservation is finished, water is added into the reaction system, and ammonia is introduced to adjust the pH value to 2.
9) After the pH value meets the requirement, the temperature is reduced to 20 ℃, and the stirring is continued for 3 hours.
10) And after the temperature reduction and crystallization are finished, filtering, and taking out part of mother liquor to be used for the next reaction. Soaking the crude IDA in water for 30min, and filtering.
2. Application scheme
1) Adding the residual mother liquor in the previous batch into a reaction kettle, adjusting the pH value to 7.0-7.5, performing primary concentration and desalting, evaporating a proper amount of water according to actual conditions, and performing primary salt discharge. Salt 1 was washed slowly with 50 water. And returning the primary concentrated mother liquor and the washing water to the reaction equipment for secondary concentration and desalination, evaporating a proper amount of water according to actual conditions, performing secondary salt discharge, and slowly washing the salt 2 with water.
2) Adding the mother liquor and sulfuric acid into the reaction system to prepare 75% sulfuric acid solution.
3) Raising the temperature to 105 ℃, slowly adding the iminodiacetonitrile reaction solution, controlling the reaction temperature to be about 110 ℃, and after the addition is finished, carrying out micro-negative pressure water distillation.
4) Continuously adding the iminodiacetonitrile reaction solution, controlling the reaction temperature to be about 115 ℃, and adding sulfuric acid after the addition is finished.
5) After the sulfuric acid is added, adding iminodiacetonitrile reaction liquid, controlling the reaction temperature to be about 115 ℃, and performing micro-negative pressure water evaporation for more than 3 hours after the addition is finished.
6) Continuously adding the iminodiacetonitrile reaction solution, controlling the reaction temperature to be about 115 ℃, and adding sulfuric acid after the addition is finished.
7) After the sulfuric acid is added, adding iminodiacetonitrile reaction liquid, controlling the reaction temperature to be about 115 ℃, and performing micro-negative pressure water evaporation for more than 3 hours after the addition is finished.
8) And (5) preserving the heat after the water evaporation is finished.
9) After the heat preservation is finished, the temperature is reduced to about 80 ℃, hydrogen peroxide is slowly added, and the heat preservation is carried out for 0.5h at the temperature of 80-90 ℃.
10) After the heat preservation is finished, water (washing water and clear water in the last batch) and concentrated mother liquor in the last batch are added into the reaction system, and ammonia is introduced to adjust the pH value to 2.
11) After the pH value meets the requirement, the temperature is reduced to 20 ℃, and the stirring is continued for 3 hours.
12) And after the temperature reduction and crystallization are finished, filtering, and taking out part of mother liquor to be used for the next reaction. Soaking the crude IDA in water for 30min, and filtering.
Sulfuric acid hydrolysis result using iminodiacetonitrile reaction liquid as raw material
The effect is that the yield of the iminodiacetonitrile in the reaction liquid IDA reaches 94.7 percent, the average content of IDA products after drying reaches 98.10 percent, the direct yield of the last three batches of products reaches more than 83.8 percent, and if the IDA amount in the mother liquid and the washing water of the products is considered, the yield of the IDA reaches more than 92 percent.
The method takes iminodiacetonitrile reaction liquid as a raw material, and obtains a qualified iminodiacetic acid product through the steps of sulfuric acid hydrolysis, decoloration, ammonia gas or ammonia water neutralization, crystallization, washing and the like, and the method is feasible in process and safe and stable in production process. And the process flow is short, the waste water is less, the environmental protection advantage is obvious, the use of sodium hydroxide is avoided, and the production cost is reduced.
The iminodiacetonitrile reaction solution is used as a raw material, the production process is simplified, a plurality of working procedures of original iminodiacetonitrile process crystallization, concentration, secondary crystallization, mother liquor sedimentation, waste liquor incineration and the like are omitted, the generation of iminodiacetonitrile products with poor quality is avoided, the total yield of IDA is greatly improved, and the method has good economic benefit.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. The method for preparing iminodiacetic acid by taking iminodiacetonitrile feed liquid as a raw material is characterized by comprising the following steps:
1) adding 65-75% by mass of sulfuric acid solution into a reaction system, adding iminodiacetonitrile feed liquid into the reaction system for hydrolysis, and decolorizing after the reaction is finished to obtain decolorized liquid, wherein the iminodiacetonitrile feed liquid is obtained by one or more of reacting hydrocyanic acid, hexamethylenetetramine and formaldehyde serving as raw materials, heating aminoacetonitrile for disproportionation reaction, reacting hydroxyacetonitrile with aminoacetonitrile, and reacting hydroxyacetonitrile and ammonia serving as raw materials;
2) adding ammonia water into a solid-liquid separation system I, transferring the obtained decolorized solution into the solid-liquid separation system I, adjusting the pH value of the feed liquid to be 1.5-3, cooling for crystallization after reaction, and separating by using a solid-liquid separation system І to obtain iminodiacetic acid and crystallization mother liquor;
3) transferring the crystallization mother liquor obtained in the step 2) into an evaporation crystallization system, introducing ammonia, adjusting the pH value of the solution to 7-7.5 for evaporation crystallization, and performing n-type separation by a solid-liquid separation system to obtain ammonium sulfate and concentrated mother liquor;
4) and 3) feeding the concentrated mother liquor obtained from the solid-liquid separation system II into a decoloring system for cyclic application to participate in the next reaction.
2. The method according to claim 1, wherein the reaction temperature in the step 1) is 100 to 120 ℃ and the decoloring temperature is 70 to 90 ℃.
3. The method according to claim 1 or 2, characterized in that activated carbon and/or hydrogen peroxide are added into the decoloring system in the step 1); the dosage of the active carbon is 1-10% of the weight of the iminodiacetic acid.
4. The method as claimed in claim 1, wherein the water evaporated in the micro-boiling state at the reaction temperature of 100-120 ℃ in the step 1) is condensed and then recycled to the decoloring system.
5. The method according to claim 1, wherein the conversion rate of the iminodiacetonitrile feed liquid in the step 1) is 90-97% and then the aminodiacetonitrile feed liquid is transferred to a decoloring system for decoloring.
6. The method as claimed in claim 1, wherein the iminodiacetic acid obtained from the solid-liquid separation system I in the step 2) is washed with water and dried to obtain the iminodiacetic acid product, and the washing water is recycled.
7. The method according to claim 1, wherein ammonia is added in the step 2) to adjust the pH value to 1.5-3; the reaction temperature is 60-80 ℃.
8. The method according to claim 1, wherein the temperature for temperature reduction and crystallization in step 2) is 10-40 ℃ and the crystallization time is 0.5-4 h.
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| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN104557580A (en) * | 2015-01-29 | 2015-04-29 | 重庆紫光化工股份有限公司 | Method for preparing iminodiacetic acid |
| KR20180056162A (en) * | 2016-11-18 | 2018-05-28 | 동우 화인켐 주식회사 | A method of iminodiacetic acid |
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