CN111620774A - Production method for preparing high-purity solid malonic acid from calcium malonate - Google Patents
Production method for preparing high-purity solid malonic acid from calcium malonate Download PDFInfo
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- CN111620774A CN111620774A CN202010343452.5A CN202010343452A CN111620774A CN 111620774 A CN111620774 A CN 111620774A CN 202010343452 A CN202010343452 A CN 202010343452A CN 111620774 A CN111620774 A CN 111620774A
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- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
Abstract
A process for preparing high-purity solid malonic acid from calcium malonate includes such steps as acidifying calcium malonate with sulfuric acid or phosphoric acid to obtain the solution of salt-containing malonic acid, solid-liquid separation, decolouring, electrodialysis or ion exchange, and refining. The main content of the produced solid malonic acid product is more than or equal to 99.5 percent, no organic solvent is contained, and the production cost is low.
Description
Technical Field
The invention relates to a production method for preparing high-purity solid malonic acid from calcium malonate, in particular to a production method for preparing low-cost high-purity solid malonic acid with the main content of more than or equal to 99.5% and without organic solvent, belonging to the field of fine chemical intermediates.
Background
Malonic acid CH2(COOH)2The product is also named as caronic acid, beet acid and malic acid, is widely applied to aspects of spices, adhesives, resin additives, medical intermediates, food additives, electroplating polishing agents, explosion control agents and the like, and is an important fine chemical intermediate.
The malonic acid product has no national standard in China, only has enterprise standard, and a common manufacturer can only achieve the main content of the product to be more than or equal to 99.0 percent and can not produce a product with higher purity. And the malonic acid product with the main content of more than or equal to 99.5 percent is generally called high-purity product. The enterprise standard (320922 MDK 001-2016) for preparing malonic acid products by hydrolyzing malonic ester, which is released by the chemical company of Maydike in salt cities, has the requirement that the main content of the products is more than or equal to 99.0 percent. The product main content of the malonic acid product enterprise standard (320116 NJSJ 248-2018) released by Nanjing chemical reagent company is required to be more than or equal to 98.5 percent. The quality enterprise standard (Q/321311 GNX 003-.
At present, the main production methods of malonic acid comprise cyanoacetate hydrolysis, malonate hydrolysis and ester exchange methods which belong to reverse-direction process, cyanoacetic acid hydrolysis which belongs to forward-direction process, and the like.
The cyanoacetate hydrolysis method, malonate hydrolysis method and ester exchange method are all reverse method processes, and the cyanoacetate and malonate are industrially used as starting materials, firstly cyanoacetic acid or malonic acid is produced and then esterified, and finally malonic acid is prepared in a reverse direction, so that the problems of long production process, large investment, low yield, high energy consumption and material consumption and high production cost exist. Although the prepared solid malonic acid has high purity and can meet the high quality requirements of industries such as medicine, spice and the like, the high cost greatly limits the application of the malonic acid in the common field.
The hydrolysis method of cyanoacetic acid is a forward process which uses monochloroacetic acid as initial raw material, firstly produces cyanoacetate, and then uses alkaline hydrolysis to obtain malonate, and then uses acidification to prepare malonic acid. Patent publication nos. CN1408697, CN1410409 and CN1858034 are that monochloroacetic acid and calcium hydroxide (or calcium oxide) are subjected to neutralization reaction to prepare calcium monochloroacetate, then the calcium monochloroacetate and hydrocyanic acid (or calcium cyanide and sodium cyanide) are subjected to cyanidation reaction to obtain calcium cyanoacetate, the calcium cyanoacetate is subjected to alkaline hydrolysis and solid-liquid separation to obtain calcium malonate solid, and the calcium malonate is obtained by acidification after separation. The patent CN1408697, CN1410409, CN1858034 provided a forward process of producing malonic acid solid by neutralizing, cyaniding, alkaline hydrolysis, and solid-liquid separation using monochloroacetic acid as the starting material, and then acidifying, the process has the advantages of short production flow, less investment, high yield, low energy and material consumption, and low production cost compared with the ester hydrolysis method and the ester exchange method, especially compared with the conventional process using sodium hydroxide and sodium cyanide as the raw materials, the process has the advantages of using cheap calcium hydroxide (calcium oxide) and calcium cyanide as the raw materials for neutralization, cyaniding, and alkaline hydrolysis, greatly reducing the production cost, and the produced calcium malonate is solid, and can be separated and purified by simple solid-liquid separation and washing, compared with the sodium method, the separation of salt with 2/3 ratio is realized in advance, the difficulty of salt separation in the subsequent process is greatly reduced, and the process is a promising method for producing malonic acid. However, the raw material calcium hydroxide (calcium oxide) used for producing calcium malonate has more impurities and impurities such as iron and heavy metals in sulfuric acid and hydrochloric acid of an acidifying agent, and acidified liquid obtained by acidifying calcium malonate with sulfuric acid and hydrochloric acid may contain magnesium ions, silicate groups, iron ions, heavy metal ions and the like besides malonic acid, calcium sulfate and sulfuric acid or malonic acid, calcium chloride and hydrochloric acid, so that the purification difficulty is very high. The patent CN1408697 and CN1410409 only show methods for obtaining crude malonic acid containing more impurities, and do not show methods for purifying and preparing high-purity solid malonic acid. Patent CN1858034 mentions "pure malonic acid aqueous solution can be obtained by separation and purification, and high purity malonic acid product can be obtained by the steps of concentration, crystallization, separation, drying, etc., but no specific purification method is given.
Patent publication No. CN103408418 proposes a method for extracting and purifying malonic acid from a salt-containing solution by using an extracting agent, wherein the extracting agent is ethyl formate, ethyl acetate, propyl acetate, methyl propionate or ethyl propionate, and the extract is subjected to reduced pressure distillation and concentration to obtain solid malonic acid with the content of more than 99.5%. The purification method has the advantages that a certain amount of extractant enters the water phase, so that the difficulty of wastewater treatment is increased; the extraction operation needs to be repeated for many times, the operation is complicated, and the consumption of the extractant is large; the lower explosion limits of the five extracting agents are lower, and the requirement on the safety protection of the device is higher; a certain amount of extractant residues exist in the solid malonic acid product, so that the downstream application of the solid malonic acid product is influenced; the main content of the product can only reach more than or equal to 99.5 percent, and the product cannot have higher purity.
The Organic Synthesis literature [ Organic Synthesis Collection ] -second volume (A.H. Blatt eds., John Wiley, New York, 1943) at page 376 discloses a process in which malonic acid is obtained by alkaline hydrolysis of cyanoacetic acid, and the salt is reacted with calcium chloride to form calcium malonate, which is then acidified to obtain malonic acid, which is extracted with an Organic solvent. The product obtained by the method also has the problems of complicated operation and solvent residue.
The patent with publication number CN1562942 proposes a method for producing high-purity malonic acid, which comprises performing ester exchange between diethyl malonate and acetic acid in pure water to obtain an aqueous solution containing malonic acid, ethyl acetate and ethanol, evaporating ethyl acetate and ethanol, decolorizing and refining to obtain high-purity solid malonic acid product with main content of 99.8% or more, and can be used for the production of downstream high-end medicines and perfumes with strict requirements on raw material quality. The process adopts diethyl malonate to carry out ester exchange in pure water, thereby not only avoiding the defect that a cyanoacetic acid hydrolysis method additionally introduces metal ions and acid radical ions, but also avoiding the problem of solvent residue of a solvent extraction method. But the price of diethyl malonate serving as a raw material is high, so that the produced high-purity malonic acid product is high in cost, and the downstream application of the high-purity malonic acid product is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a production method for preparing high-purity solid malonic acid from calcium malonate, in particular a production method for preparing low-cost high-purity solid malonic acid with the main content of more than or equal to 99.5% by purifying a salt-containing malonic acid solution and without containing an organic solvent.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
(1) adding water into the calcium malonate solid, pulping, adding sulfuric acid or phosphoric acid, carrying out an acidification reaction to obtain an acidification liquid containing the malonic acid and calcium sulfate solid or calcium phosphate solid, and carrying out solid-liquid separation on the acidification liquid to obtain an acidification filtrate and the calcium sulfate solid or calcium phosphate solid;
(2) refining and purifying the acidified filtrate by an ion exchange resin column or electrodialysis to obtain a pure malonic acid solution, wherein the content of calcium ions in the refined and purified feed liquid is less than 0.05wt%, the content of sulfate ions is less than 0.03wt% or the content of phosphate ions is less than 0.02%;
(3) dehydrating and drying the pure malonic acid solution to obtain a high-purity solid malonic acid product.
According to the technical scheme, the calcium malonate solid in the step (1) is added with water and pulped, and the added water amount is 0.5-8 times of the mass of the calcium malonate solid.
The technical scheme is that in the step (1), the concentration of sulfuric acid is 10-70%, and the concentration of phosphoric acid is 10-60%.
The acidification reaction in the step (1) of the technical scheme is characterized in that the content of free calcium ions in feed liquid is controlled to be less than or equal to 0.30wt% at the end point.
The reaction equation of the acidification reaction of calcium malonate and sulfuric acid to obtain the malonic acid and the calcium sulfate is as follows:
CH2(COO) 2Ca+H2SO4→ CH2(COOH) 2+ CaSO4↓
the reaction equation of the acidification reaction of calcium malonate and phosphoric acid to obtain malonic acid and calcium phosphate is as follows:
CH2(COO) 2Ca+2/3H3PO4→ CH2(COOH) 2+ 1/3Ca3(PO4)2↓
the technical scheme is that the solid-liquid separation in the step (1) comprises centrifugal separation, filter pressing, suction filtration and the like.
Further, in the step (1) of the technical scheme, the separated calcium sulfate solid or calcium phosphate solid is washed by water, and the washing water is combined into the acidified filtrate to enter the next working procedure.
Further, in the technical scheme, in the step (2), after adding an adsorbent into the acidified filtrate for decolorization and separating adsorbent residues, the acidified filtrate enters an ion exchange resin column or homogeneous membrane electrodialysis for treatment. The adsorbent is one or a combination of more of diatomite, a pure silicon microporous molecular sieve, natural zeolite or artificially synthesized zeolite molecular sieve and active carbon, and comprises modified varieties of the diatomite, the pure silicon microporous molecular sieve, the natural zeolite or the artificially synthesized zeolite molecular sieve and the active carbon. The activated carbon is powdered activated carbon, granular activated carbon, activated carbon fiber or a combination thereof.
The ion exchange resin column in the step (2) can be a compound bed or a mixed bed; the cation exchange resin is H type strong acid cation exchange resin, and the anion exchange resin is OH type strong base anion exchange resin.
Furthermore, the anion and cation exchange resin is regenerated by adopting an electric regeneration technology, so that the problem that a large amount of waste acid and alkali is generated by adopting an acid-alkali regeneration technology in the prior art is solved, and clean regeneration is realized.
The electrodialysis in the step (2) of the technical scheme refers to heterogeneous membrane packed bed-free electrodialysis, homogeneous membrane packed bed-free electrodialysis and homogeneous membrane packed bed electrodialysis. The packed bed electrodialysis refers to electrodialysis filled with anion-cation exchange resin in a dilute chamber.
According to the technical scheme, the temperature of a feed liquid in the electrodialysis purification process in the step (2) is controlled to be 5-40 ℃, and the pH value of the feed liquid is controlled to be 0.5-3.5.
Further, the brine from the electrodialysis concentration chamber is returned for pulping of calcium malonate or for preparing sulfuric acid or phosphoric acid for acidification.
The technical scheme is that the pure malonic acid solution obtained in the step (3) is dehydrated and dried to obtain a high-purity solid malonic acid product, and the method comprises the following steps: the pure malonic acid solution is subjected to negative pressure evaporation concentration, cooling crystallization, solid-liquid separation, vacuum drying and other processes to obtain a high-purity solid malonic acid product.
The main content of the high-purity solid malonic acid product obtained in the step (3) of the technical scheme is more than or equal to 99.5%.
The invention has the beneficial effects that:
1) the production method for preparing the high-purity solid malonic acid from calcium malonate, calcium monochloroacetate, calcium hydroxide (calcium oxide) and calcium cyanide (hydrocyanic acid + calcium hydroxide or calcium oxide) serving as raw materials through neutralization, cyanidation, alkaline hydrolysis and solid-liquid separation has low production cost, so that the production method for preparing the high-purity solid malonic acid from the calcium malonate not only avoids the problems of complicated extraction operation, flammability and explosive safety of a solvent and the problem of containing the solvent in a product in a solvent extraction method, but also can ensure that the quality of the malonic acid product can reach or even be superior to the existing high-cost ester hydrolysis method and ester exchange method process, thereby providing a production route for the high-purity solid malonic acid product which is shorter, saves investment, has higher yield, is lower in material consumption and energy consumption and is lower in production cost, and compared with the ester hydrolysis method and ester exchange method processes, the production cost can be reduced by.
2) The produced low-cost high-purity solid malonic acid product can greatly reduce the production cost of downstream medicines and spices, and can realize the exploitation of new product application by the advantages.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is illustrated below by way of examples, but the present invention is not limited to these examples.
Example 1: 519.1g of calcium malonate and water with the mass 1.5 times of that of calcium malonate are put into an acidification reaction kettle to be stirred and pulped, 1197.24g of 35% sulfuric acid is dripped into the acidification reaction kettle at 52 ℃, after the reaction is finished, the calcium sulfate filter cake is filtered and washed by water, the washing water and the filtrate are combined to obtain an acidification liquid, the pH value of the feed liquid is adjusted to 1.5, a certain amount of activated carbon fiber is added for decolorization, activated carbon residue is filtered out and is subjected to fine filtration treatment, electrodialysis purification is carried out at 26 ℃ by adopting a homogeneous membrane non-packed bed to obtain a pure malonic acid aqueous solution, and the content of calcium ions in the feed liquid is less than 0.05wt% and the content. And returning the brine obtained from the electrodialysis concentration chamber to the acidification reaction kettle for pulping the calcium malonate. The malonic acid aqueous solution is evaporated and concentrated under negative pressure, cooled and crystallized, centrifugally separated and dried in vacuum to obtain 323.43g of high-purity solid malonic acid product with the main content of more than or equal to 99.5 percent.
Example 2: 572.53g of calcium malonate and water with the mass 3.2 times of that of calcium malonate are put into an acidification reaction kettle to be stirred and pulped, 1024.2g of 30% phosphoric acid is dripped into the acidification reaction kettle at 60 ℃, after the reaction is finished, the calcium phosphate filter cake is filtered and washed by water, the washing water and the filtrate are combined to obtain an acidification liquid, a certain amount of modified diatomite is added for decolorization, the modified diatomite is filtered to remove the modified diatomite slag and is subjected to fine filtration, the filtration is carried out on the modified diatomite slag, the filtration is carried out, the purification is carried out on the modified diatomite slag in a mixed bed of ion exchange resin columns, and a pure malonic acid aqueous solution is obtained. The ion exchange resin is regenerated using electrical regeneration techniques. The malonic acid aqueous solution is evaporated and concentrated under negative pressure, cooled and crystallized, centrifugally separated and dried in vacuum to obtain 358.70g of high-purity solid malonic acid product with the main content of more than or equal to 99.5 percent.
Claims (10)
1. A production method for preparing high-purity solid malonic acid from calcium malonate is characterized by comprising the following steps:
(1) adding water into the calcium malonate solid, pulping, adding sulfuric acid or phosphoric acid, carrying out an acidification reaction to obtain an acidification liquid containing the malonic acid and calcium sulfate solid or calcium phosphate solid, and carrying out solid-liquid separation on the acidification liquid to obtain an acidification filtrate and the calcium sulfate solid or calcium phosphate solid;
(2) refining and purifying the acidified filtrate by an ion exchange resin column or electrodialysis to obtain a pure malonic acid solution, wherein the content of calcium ions in the refined and purified feed liquid is less than 0.05wt%, the content of sulfate ions is less than 0.03wt% or the content of phosphate ions is less than 0.02%;
(3) dehydrating and drying the pure malonic acid solution to obtain a high-purity solid malonic acid product.
2. The production method for preparing the high-purity solid malonic acid from the calcium malonate according to claim 1, characterized in that water is added into the calcium malonate solid in the step (1) for pulping, and the added water amount is 0.5-8 times of the mass of the calcium malonate solid.
3. The method for preparing the high-purity solid malonic acid from the calcium malonate according to claim 1, wherein the concentration of sulfuric acid used in the acidification reaction in the step (1) is 10-70%, and the concentration of phosphoric acid used in the acidification reaction is 10-60%.
4. The method for preparing high-purity solid malonic acid from calcium malonate according to claim 1, wherein the free calcium ion content in the acidification reaction end point control feed liquid in the step (1) is less than or equal to 0.30 wt%.
5. The method for preparing the high-purity solid malonic acid from the calcium malonate according to the claim 1, wherein the acidified filtrate obtained in the step (2) is decolorized by adding an adsorbent and then treated by ion exchange resin column or homogeneous membrane electrodialysis after separating adsorbent residues; the adsorbent is one or a combination of more of diatomite, a pure silicon microporous molecular sieve, natural zeolite or artificially synthesized zeolite molecular sieve and active carbon, and comprises modified varieties of the diatomite, the pure silicon microporous molecular sieve, the natural zeolite or the artificially synthesized zeolite molecular sieve and the active carbon; the activated carbon is powdered activated carbon, granular activated carbon, activated carbon fiber or a combination thereof.
6. The method for producing high-purity solid malonic acid from calcium malonate according to claim 1, wherein the electrodialysis in step (2) refers to heterogeneous membrane non-packed bed electrodialysis, homogeneous membrane non-packed bed electrodialysis and homogeneous membrane packed bed electrodialysis.
7. The production method for preparing high-purity solid malonic acid from calcium malonate according to claim 1, wherein the feed liquid temperature in the electrodialysis purification process in the step (2) is controlled to be 5-40 ℃, and the pH value of the feed liquid is controlled to be 0.5-3.5.
8. The method for preparing the high-purity solid malonic acid from the calcium malonate according to the claim 1, wherein the ion exchange resin column in the step (2) can be a compound bed or a mixed bed; the cation exchange resin is H type strong acid cation exchange resin, and the anion exchange resin is OH type strong base anion exchange resin.
9. The method for producing high-purity solid malonic acid from calcium malonate according to claims 1 and 8, wherein the anion-cation exchange resin is regenerated by an electrical regeneration technology.
10. The method for producing the high-purity solid malonic acid from the calcium malonate according to claim 1, wherein the high-purity solid malonic acid product obtained in the step (3) has a main content of more than or equal to 99.5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11326191B2 (en) * | 2016-11-14 | 2022-05-10 | Lygos, Inc. | Process for purification of malonic acid from fermentation broth |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11326191B2 (en) * | 2016-11-14 | 2022-05-10 | Lygos, Inc. | Process for purification of malonic acid from fermentation broth |
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