阅读说明：本技术 一种碳酸氢铵的提纯方法 (Method for purifying ammonium bicarbonate ) 是由 邓毅 李颜利 李伟 邹伟 郑汶江 马小燕 杨虎 颜杰 张海波 李慧 刘波 于 2020-06-05 设计创作，主要内容包括：本发明公开了一种碳酸氢铵的提纯方法,采用D201树脂制备吸附柱,将碳酸氢铵溶液由吸附柱上方加入,并收集吸附柱下方碳酸氢铵溶液,并经冷冻干燥,得到高纯度的碳酸氢铵。所述树脂经过预处理,其预处理方法为：将树脂用去离子水浸泡24h；再用NaOH水溶液处理,处理完毕后用水清洗；然后经过第一盐酸溶液处理,并用清水洗至中性；最后用硫代硫酸钠和EDTA处理,用清水洗至中性。本发明能够有效解决碳酸氢铵容易分解,并且提纯后母液中还有大量碳酸氢铵导致原料浪费的问题,并且快速、环保、无二次污染,制得碳酸氢铵纯度高达99.9%以上,并且操作简单易行、绿色环保。(The invention discloses a purification method of ammonium bicarbonate, which adopts D201 resin to prepare an adsorption column, adds an ammonium bicarbonate solution from the upper part of the adsorption column, collects the ammonium bicarbonate solution from the lower part of the adsorption column, and obtains high-purity ammonium bicarbonate through freeze drying. The resin is pretreated, and the pretreatment method comprises the following steps: soaking the resin in deionized water for 24 hours; then treating with NaOH aqueous solution, and cleaning with water after the treatment is finished; then treating the mixture by using a first hydrochloric acid solution, and washing the mixture to be neutral by using clear water; finally, the mixture is treated by sodium thiosulfate and EDTA and washed by clear water to be neutral. The method can effectively solve the problems that the ammonium bicarbonate is easy to decompose and a large amount of ammonium bicarbonate in the purified mother liquor causes raw material waste, is quick, environment-friendly and free of secondary pollution, and the purity of the prepared ammonium bicarbonate is up to more than 99.9 percent, and is simple and easy to operate and environment-friendly.)

1. A method for purifying ammonium bicarbonate is characterized in that D201 resin is adopted to prepare an adsorption column, an ammonium bicarbonate solution is added from the upper part of the adsorption column, the ammonium bicarbonate solution below the adsorption column is collected, and freeze drying is carried out to obtain high-purity ammonium bicarbonate.

2. The method for purifying ammonium bicarbonate according to claim 1, wherein the resin is pretreated by: soaking the resin in deionized water for 24 hours; then treating with NaOH aqueous solution, and cleaning with water after the treatment is finished; then treating the mixture by using a first hydrochloric acid solution, and washing the mixture to be neutral by using clear water; and finally, treating the mixture for 0.5 to 10 hours by using a mixed solution of sodium thiosulfate and EDTA, and washing the mixture to be neutral by using clear water.

3. The method for purifying ammonium bicarbonate according to claim 2, wherein the concentration of the NaOH aqueous solution is 1-5%, the treatment volume is 5-10 times of the resin volume, and the resin is washed with 10-20 times of deionized water.

4. The method of claim 2, wherein the concentration of the first hydrochloric acid solution is 0.5% to 8%, and the treatment volume is 5 to 10 times the resin volume.

5. The method for purifying ammonium bicarbonate according to claim 2, wherein the amount of the sodium thiosulfate is 1% to 20% of the mass of the resin, and the amount of the EDTA is 0.5% to 25% of the mass of the resin.

6. The method for purifying ammonium bicarbonate according to claim 1, wherein the ammonium bicarbonate content in the added ammonium bicarbonate solution is 99.4-99.5%, the ammonium bicarbonate cannot be purified to 99.9% by a conventional purification method such as recrystallization, and the leaching solution outflow rate is 30-100 mL/h.

7. The method for purifying ammonium bicarbonate according to any one of claims 1 to 6, further comprising a desorption regeneration process of the adsorption column, wherein the desorption regeneration process comprises the following steps: and adding a second hydrochloric acid solution from the upper part of the adsorption column for washing, wherein the adding speed of the second hydrochloric acid solution is consistent with the speed of the ammonium bicarbonate solution during adsorption until the effluent liquid is not red when being detected by a potassium thiocyanate solution after being acidified, and then washing by distilled water, so that the adsorption material is regenerated.

8. The method for purifying ammonium bicarbonate according to claim 7, wherein the concentration of the second hydrochloric acid solution is 0.1-5 mol/L, the amount of the second hydrochloric acid solution is 2-5 times of the volume of the resin, and the treatment time is 1-10 h.

9. The method for purifying ammonium bicarbonate according to claim 7, wherein the amount of the distilled water is 3 to 5 times of the volume of the resin.

Technical Field

The invention relates to the technical field of inorganic salt purification, in particular to a method for purifying ammonium bicarbonate.

Background

Ammonium bicarbonate (NH)₄HCO₃) Also called ammonium bicarbonate, is a white monoclinic or orthorhombic crystal system crystal with a molecular weight of 79.1 and a theoretical nitrogen content of 17.72 percent, and is an inorganic salt with wide application. Can be used as a nitrogen fertilizer in agriculture, is suitable for various soils, can simultaneously provide ammonium nitrogen and carbon dioxide required by the growth of crops, can promote the growth and photosynthesis of the crops, promote the seedlings and grow leaves, and can be used as a top dressing and a base fertilizer for direct application. Can be used as high-grade leavening agent in food, and can be used as leavening agent for bread, cookies, battercake, etc. in combination with sodium bicarbonate, and also used as raw material of foaming powder fruit juice, and used for blanching green vegetables, bamboo shoot, etc. And medicines and reagents, and the fermentation powder also takes the product as a main component and is matched with an acidic substance. In pharmaceutical applicationsIn addition, the introduction of ammonium bicarbonate can improve the distribution proportion of HPCT, prolong the retention time of the medicine in lung, improve the curative effect of HPCT on lung cancer and the like. The current environments of various industries all require that ammonium bicarbonate series products continuously explore new processing techniques and novel ammonium bicarbonate products to adapt to the standards of corresponding industries while taking the inherent value of the ammonium bicarbonate series products into consideration and stabilizing the market status of the ammonium bicarbonate series products. In order to better meet the requirements of more fields, the purity of the ammonium bicarbonate is required to be improved.

Currently, ammonium bicarbonate is mainly prepared by a crystallization method, and ammonium bicarbonate is separated out from a solution by utilizing solubility difference. However, the crystallization method for preparing ammonium bicarbonate has the following disadvantages: 1. in the crystallization process, the loss amount of ammonium bicarbonate is large, and a large amount of ammonium bicarbonate is contained in the mother liquor, so that waste is easily caused. 2. Because the ammonium bicarbonate is decomposed into carbon dioxide, ammonia and water at the temperature of over 36 ℃, the ammonium bicarbonate can be completely decomposed at the temperature of 60 ℃, the temperature is high in the crystallization process, the separated ammonium bicarbonate is easy to decompose, the yield of the ammonium bicarbonate is reduced, the preparation cost of the ammonium bicarbonate is high, and the industrial production is not facilitated. 3. The ammonium bicarbonate purified by the crystallization method contains impurities such as metal ions, and is difficult to remove from the ammonium bicarbonate formed by the crystallization, so that the purity of the ammonium bicarbonate is not high.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to solve the problems that the mother liquor after crystallization contains a large amount of ammonium bicarbonate, the mother liquor is difficult to be completely utilized, the crystallization temperature is high, and the ammonium bicarbonate is easy to decompose in the conventional crystallization method for preparing the ammonium bicarbonate, and provides a method for purifying the ammonium bicarbonate.

In order to solve the technical problems, the invention adopts the following technical scheme:

a process for purifying ammonium hydrogen carbonate includes such steps as preparing adsorption column with D201 resin, adding ammonium hydrogen carbonate solution from the top of adsorption column, collecting the ammonium hydrogen carbonate solution from the bottom of adsorption column, and freeze drying.

Wherein, the resin is pretreated, and the pretreatment method comprises the following steps: soaking the resin in deionized water for 24 hours; then treating with NaOH aqueous solution, and cleaning with water after the treatment is finished; then treating the mixture by using a first hydrochloric acid solution, and washing the mixture to be neutral by using clear water; and finally, treating the mixture for 0.5 to 10 hours by using a mixed solution of sodium thiosulfate and EDTA (ethylene diamine tetraacetic acid), and washing the mixture to be neutral by using clear water.

Further, the concentration of the NaOH aqueous solution is 1% -5%, the treatment volume is 5-10 times of the volume of the resin, and then the resin is cleaned by deionized water of 10-20 times.

Further, the concentration of the first hydrochloric acid solution is 0.5-8%, and the treatment volume is 5-10 times of the volume of the resin.

Furthermore, the dosage of the sodium thiosulfate accounts for 1-20% of the mass of the resin, and the dosage of the EDTA accounts for 0.5-25% of the mass of the resin.

Further, the content of ammonium bicarbonate in the added ammonium bicarbonate solution is 99.4-99.5%, and the leaching solution outflow rate is 30-100 mL/h.

Further, still include the desorption regeneration process of adsorption column, desorption regeneration process is: and adding a second hydrochloric acid solution from the upper part of the adsorption column for washing, wherein the adding speed of the second hydrochloric acid solution is consistent with the speed of the ammonium bicarbonate solution during adsorption until the effluent liquid is not red when being detected by a potassium thiocyanate solution after being acidified, and then washing by distilled water, so that the adsorption material is regenerated.

Further, the concentration of the second hydrochloric acid solution is 0.1-5 mol/L, the using amount of the second hydrochloric acid solution is 2-5 times of the volume of the resin, and the treatment time is 1-10 hours.

Further, the washing amount of the distilled water is 3-5 times of the volume of the resin.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention adopts a resin adsorption mode to purify ammonium bicarbonate, and adopts pretreated D201 resin to prepare an adsorption column. D201 is styrene-divinylbenzene copolymer with macroporous structure and quaternary ammonium group [ -N (CH)₃)₃OH]The anion exchange resin of (4) is capable of adsorbing a plurality of ions (mainly comprising Fe) in the ammonium bicarbonate solution²⁺And Fe³⁺) Therefore, the ammonium bicarbonate solution can be purified, and has the advantages of difficult poisoning, high exchange speed,The stability is good. Effectively solves the problems that the ammonium bicarbonate is easy to decompose and a large amount of ammonium bicarbonate in the mother liquor after purification causes waste of raw materials.

2. The invention carries out adsorption purification by utilizing the pretreated resin, and has the advantages of high efficiency, simple operation, easily obtained materials and recyclable materials. In the conventional purification method in the prior art, such as a recrystallization method, the purity of the purified ammonium bicarbonate is 99.4-99.5%, but the purification method provided by the invention has high economic benefit, the purity of the prepared ammonium bicarbonate is more than 99.94%, and the method is simple and easy to operate, green and environment-friendly.

3. The invention also provides a step of desorption regeneration of the resin, and the resin after adsorption is saturated and can be regenerated by treatment of hydrochloric acid solution, so that the resin can be recycled, the purification cost of ammonium bicarbonate is reduced, and the method is suitable for industrial production.

Drawings

FIG. 1 is a process flow diagram of a purification method of ammonium bicarbonate of the present invention.

Detailed Description

The invention will be further explained with reference to the drawings and the embodiments.