CN100516016C - Process for the preparation of malonic ester - Google Patents
Process for the preparation of malonic ester Download PDFInfo
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- CN100516016C CN100516016C CNB2006100542547A CN200610054254A CN100516016C CN 100516016 C CN100516016 C CN 100516016C CN B2006100542547 A CNB2006100542547 A CN B2006100542547A CN 200610054254 A CN200610054254 A CN 200610054254A CN 100516016 C CN100516016 C CN 100516016C
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Abstract
The invention refers to Method for preparation of malonic ester which using chloroacetic acid as raw materal. It uses chloroacetic acid as material, containing neutralization reaction, cyanidation reaction, acidification reaction, dehydration and esterification reaction, the charaters lies in: the adopted liquid sodium cyanide of the mentioned cyanidation reaction is produced by adding hydrocyanic acid forming gas in caustic soda solution of 35- 40 wet% to do synthesis reaction.This invention avoids the step of using dilute sulphuric acid to absorb, and then to distillation prepare liquid hydrocyanic acid in order to remove carbon dioxide in current technology of hydrocyanic acid forming gas, making the technique is shorter, the cost is lower, more safe and environmental protection than before, is very suit to commercial cleaning manufacture.
Description
Technical field
The present invention relates to a kind of malonic ester preparation method, particularly a kind of is the method for feedstock production malonic ester with the Mono Chloro Acetic Acid.
Background technology
The malonic ester series products is the industrial raw material that is widely used in medicine, agricultural chemicals and makeup as dimethyl malonate.Malonic ester can become cyanoacetic acid with hcl acidifying by cyanoacetic acid sodium in the prior art, latter's hydrolysis and preparing in the presence of the alcohol of producing required ester (referring to " industrial organic synthesis basis " the 412nd page of Yang Jin ancestor, Sinopec press, in December, 1998), also can add this conventional route of pure esterification by propanedioic acid in addition obtains.
In addition, WO/08988, JP-A-59-7135, JP-A-59-7136, JP-B-55-41227, US-A-2337858 are by the hydrolysis in the presence of strong acid such as sulfuric acid, hydrochloric acid of cyanoacetic acid or its salt such as sodium salt, the method for producing propanedioic acid or its ester.
Yet the starting raw material sodium cyanide that relates in these prior aries, in preparation process, its quality all there is certain requirement, major cause is if the too high levels of yellow soda ash and sodium hydroxide will inevitably influence cyanogenation in the sodium cyanide, and the yield of product malonic ester is significantly dropped to below 65%.
The content about 0.6% of carbonic acid gas in Sweet natural gas ammonia oxidation method (iS-One method) the prussic acid synthetic gas, directly with iS-One method prussic acid synthetic gas and sodium hydroxide prepared in reaction liquid sodium cyanide, the content of yellow soda ash can not be directly used in the production of malonic ester 4～6% in the liquid sodium cyanide that is obtained.Therefore, past, iS-One method prussic acid manufacturing enterprise will produce the liquid sodium cyanide that is used for malonic ester, just must absorb prussic acid in the synthetic gas with dilute sulphuric acid, rectifying again, cooling, after being refined into liquid hydrogen cyanide, again with sodium hydroxide prepared in reaction liquid sodium cyanide, the result can cause the liquid sodium cyanide production link to increase, potential safety hazard increases, and production cost is higher.
Summary of the invention
The object of the present invention is to provide the malonic ester preparation method that a kind of technological process of production is simple, cost is low, product yield is high.
The object of the present invention is achieved like this: a kind of malonic ester preparation method, it is to be raw material with the Mono Chloro Acetic Acid, comprise neutralization reaction, cyanogenation, acidification reaction, dehydration and esterification, it is characterized in that: the liquid sodium cyanide raw material that adopts in the described cyanogenation is by being to feed iS-One method prussic acid synthesis gas in 35～40% the aqueous sodium hydroxide solution to carry out making after the building-up reactions to weight percent content.
The synthesis reaction temperature of aforesaid liquid sodium cyanide is controlled at 30～60 ℃; The content of sodium hydroxide is reached home less than 0.8% afterreaction in the above-mentioned building-up reactions.
The aforesaid liquid sodium cyanide is handled with calcium chloride solution before being used for cyanogenation, makes yellow soda ash and sodium hydroxide reaction in itself and the liquid sodium cyanide generate precipitation of calcium carbonate and calcium hydroxide precipitation respectively; And then to join with the Mono Chloro Acetic Acid be raw material through in the cyanogenation after the neutralization reaction, and cyanogenation finishes, and cooling removes by filter wherein precipitation of calcium carbonate and the sedimentary mixture of calcium hydroxide below 60 ℃.Perhaps remove by filter wherein precipitation of calcium carbonate and the sedimentary mixture of calcium hydroxide earlier, joining with the Mono Chloro Acetic Acid is that raw material is through in the cyanogenation after the neutralization reaction again.
The weight percent concentration of above-mentioned calcium chloride solution is 20～30%; The usage quantity of above-mentioned calcium chloride solution: in the calcium chloride solution in calcium chloride and the liquid sodium cyanide mol ratio of contained yellow soda ash be 1: 1.0～1.4, be preferably 1: 1.15～1.25.
Specifically, the present invention is by being to feed iS-One method prussic acid synthesis gas in 35～40% the aqueous sodium hydroxide solution to carry out building-up reactions at weight percent content, and temperature of reaction is controlled at 30～60 ℃; The reaction of synthetic fluid sodium cyanide is reached home after the content of sodium hydroxide in the reaction is less than 0.8%; Then the liquid sodium cyanide that makes being added weight percent concentration is that 20～30% calcium chloride solution is handled, the usage quantity of wherein said calcium chloride solution: in the calcium chloride solution in calcium chloride and the liquid sodium cyanide mol ratio of contained yellow soda ash be 1: 1.0～1.4, be preferably 1: 1.15～1.25, make yellow soda ash and sodium hydroxide reaction in calcium chloride and the liquid sodium cyanide generate precipitation of calcium carbonate and calcium hydroxide precipitation, join with the Mono Chloro Acetic Acid is that raw material is through in the cyanogenation after the neutralization reaction again, cyanogenation finishes, cooling is below 60 ℃, remove by filter wherein precipitation of calcium carbonate and the sedimentary mixture of calcium hydroxide after carry out acidification reaction again, the dehydration and esterification obtain malonic ester.
Perhaps, after removing by filter precipitation of calcium carbonate and calcium hydroxide precipitation mixture wherein earlier, joining with the Mono Chloro Acetic Acid is raw material again, in the cyanogenation after the neutralization reaction, cyanogenation finishes and carries out acidification reaction again, and dehydration and esterification obtain malonic ester.
Employed liquid sodium cyanide has requirement to the quality index of sodium cyanide without exception in the existing method that prepare malonic ester, and wherein the carbonate content requirement is less than 0.2%, and the content requirement of sodium hydroxide is less than 0.8%.This is because the too high levels of yellow soda ash and sodium hydroxide will inevitably influence cyanogenation, and the yield of product is significantly descended.The inventor is by experiment discovery repeatedly, to use weight percent content is that 30% liquid sodium cyanide is the feedstock production malonic ester, if the every rising 0.1% of the content of yellow soda ash in the sodium cyanide, the yield of malonic ester descends more than 0.3%, the every rising 0.1% of sodium hydrate content, yield decline 0.4% (all by weight percentage) of malonic ester.
The inventor has carried out research with great concentration to malonic ester preparation method, found that and adopt the direct and sodium hydroxide prepared in reaction liquid sodium cyanide of iS-One method prussic acid synthetic gas, by adding calcium chloride, can make malonic ester with high yield again to remove lime carbonate and calcium hydroxide precipitation wherein.
Key of the present invention is to have adopted the liquid sodium cyanide of and sodium hydroxide prepared in reaction direct by iS-One method prussic acid synthetic gas.And iS-One method synthetic prussic acid gas contains carbonic acid gas, prussic acid gas directly fed prepare sodium cyanide in the aqueous sodium hydroxide solution, will inevitably generate yellow soda ash, carbonate content in the prepared liquid sodium cyanide is generally 4～6%, the content of sodium hydroxide is less than 0.8%, can not be directly used in the production of malonic ester, must be handled.So, the present invention joins iS-One method prussic acid synthetic gas directly with (yellow soda ash is 4～6% in the liquid sodium cyanide of sodium hydroxide reaction generation with calcium chloride, the content of sodium hydroxide is less than 0.8%), yellow soda ash and sodium hydroxide will generate lime carbonate and calcium hydroxide precipitation with the calcium chloride reaction, remove by filter wherein precipitation, thereby yellow soda ash and sodium hydroxide are to the influence of cyanogenation in the elimination liquid sodium cyanide, and the result makes the yield of malonic ester higher.The present invention has avoided that iS-One method prussic acid synthetic gas absorbs with dilute sulphuric acid in the prior art, rectifying prepares liquid hydrogen cyanide again, thereby remove the step of carbonic acid gas, make technical process shorter, cost is lower, safer, environmental protection (because of the liquid hydrogen cyanide severe toxicity, the dilute sulphuric acid absorption liquid needs regularly to handle), and be fit to very much the industrialization cleaner production.
Embodiment
The present invention is described by the following examples, but the invention is not restricted to these embodiment.
Embodiment 1
To weight percent content is feeding iS-One method prussic acid synthesis gas in 40% the sodium hydroxide solution (sodium hydroxide 345kg folding hundred amounts 3.45 kilomols), 40～60 ℃ of control reaction temperature, after the sodium hydrate content in the reaction solution is less than 0.8%, reaction is reached home, obtain liquid sodium cyanide 451kg, sodium cyanide content 32.74% in the prepared after testing sodium cyanide solution, carbonate content 4.53%, sodium hydrate content 0.54%.
Calcium Chloride Powder Anhydrous 25kg is added water 100kg dissolve, to stating in the sodium cyanide solution, stirring reaction is 10～30 minutes under the normal temperature in the adding.With industrial Mono Chloro Acetic Acid 290kg (content 98%, folding hundred amounts are in 3 kilomols) use the 300kg water dissolution, and under the refrigerative situation, be neutralized to the sodium chloroacetate solution that pH=6.5～7.0 are mixed with saturated solution of sodium carbonate, join in the above-mentioned sodium cyanide solution, be warming up to 50 ℃, cause cyanogenation, after the cyanogenation temperature reaches 85～90 ℃, stop heating, when the cyanogenation temperature reaches 105～115 ℃, cool to 58 ℃.Remove by filter the precipitation mixture of lime carbonate and calcium hydroxide, filtrate adds 30% technical hydrochloric acid 365kg acidifying, obtains the mixed aqueous solution of cyanoacetic acid and sodium-chlor.Under the vacuum water being taken off to the greatest extent, obtain the mixture of cyanoacetic acid and sodium-chlor, cool to 60～70 ℃, still is flow state but stir down.Drop into methyl alcohol 240kg, under 60～70 ℃, slowly splash into 98% industrial vitriol oil 460kg.After dripping, make temperature of reaction reach 100 ℃ in 5 hours, add entry 700kg dissolved salt, through sedimentation, phase-splitting, tell organic phase, through neutralization, washing layering, tell neutral organic phase, get finished product 303kg through underpressure distillation, through the content 99.41% of gas chromatographic analysis dimethyl malonate, yield 76.07%.
Embodiment 2
The preparation of liquid sodium cyanide is identical with embodiment 1, Calcium Chloride Powder Anhydrous 25kg is added water 100kg to be dissolved, in the adding to stating in the sodium cyanide solution, stirring reaction is 10～30 minutes under the normal temperature, remove by filter the precipitation mixture of lime carbonate and calcium hydroxide, filter residue will be used for cyanogenation after washing lotion and the filtrate merging with the washing of 50kg clear water.
With industrial Mono Chloro Acetic Acid 290kg (content 98%, folding hundred amounts are in 3 kilomols) use the 300kg water dissolution, and under the refrigerative situation, be neutralized to the sodium chloroacetate solution that pH=6.5～7.0 are mixed with saturated solution of sodium carbonate, join in the sodium cyanide solution after treatment, be warming up to 50 ℃, cause cyanogenation, after the cyanogenation temperature reaches 85～90 ℃, stop heating, when the cyanogenation temperature reaches 105～115 ℃, cool to 55 ℃, add 30% technical hydrochloric acid 365kg acidifying, obtain the mixed aqueous solution of cyanoacetic acid and sodium-chlor.Under the vacuum water being taken off to the greatest extent, obtain the mixture of cyanoacetic acid and sodium-chlor, cool to 60～70 ℃, still is flow state but stir down.Drop into methyl alcohol 240kg, under 60～70 ℃, slowly splash into 98% industrial vitriol oil 460kg.After dripping, make temperature of reaction reach 100 ℃ in 5 hours, add entry 700kg dissolved salt, through sedimentation, phase-splitting, tell organic phase, through neutralization, washing layering, tell neutral organic phase, get finished product 296kg through underpressure distillation, through the content 99.16% of gas chromatographic analysis dimethyl malonate, yield 74.1%.
Embodiment 3
Replace methyl alcohol in industrial alcohol (100%) 370kg, all the other obtain pure product 366kg at last with embodiment 1, through the content 99.21% of gas chromatographic analysis diethyl malonate, yield 75.6%.
Embodiment 4
Replace methyl alcohol in propyl alcohol (100%) 450kg, all the other obtain pure product 430.2kg at last with embodiment 1, through the content 98.91% of gas chromatographic analysis dipropyl malonate, yield 75.4%.
Embodiment 5
Replace methyl alcohol in Virahol (100%) 450kg, all the other obtain pure product 421kg at last with embodiment 1, through the content 99.35% of gas chromatographic analysis Diisopropyl malonate, yield 74.2%.
Claims (5)
1, a kind of malonic ester preparation method, it is to be raw material with the Mono Chloro Acetic Acid, comprise neutralization reaction, cyanogenation, acidification reaction, dehydration and esterification, it is characterized in that: the liquid sodium cyanide raw material that adopts in the described cyanogenation is by being to feed iS-One method prussic acid synthesis gas in 35～40% the aqueous sodium hydroxide solution to carry out making after the building-up reactions to weight percent content; The synthesis reaction temperature of wherein said liquid sodium cyanide is controlled at 30～60 ℃; The content of sodium hydroxide is less than 0.8% in the described building-up reactions, and reaction is reached home; And described liquid sodium cyanide is handled with calcium chloride solution before being used for cyanogenation, makes yellow soda ash and sodium hydroxide reaction in itself and the liquid sodium cyanide generate precipitation of calcium carbonate and calcium hydroxide precipitation respectively; And then to join with the Mono Chloro Acetic Acid be raw material through in the cyanogenation after the neutralization reaction, and cyanogenation finishes, and cooling removes by filter wherein precipitation of calcium carbonate and the sedimentary mixture of calcium hydroxide below 60 ℃; Or remove by filter wherein precipitation of calcium carbonate and the sedimentary mixture of calcium hydroxide earlier, joining with the Mono Chloro Acetic Acid is that raw material is through in the cyanogenation after the neutralization reaction again.
2, malonic ester preparation method as claimed in claim 1 is characterized in that: the weight percent concentration of described calcium chloride solution is 20～30%; The usage quantity of described calcium chloride solution: in the calcium chloride solution in calcium chloride and the liquid sodium cyanide mol ratio of contained yellow soda ash be 1: 1.0～1.4.
3, malonic ester preparation method as claimed in claim 2 is characterized in that: the usage quantity of described calcium chloride solution: in the calcium chloride solution in calcium chloride and the liquid sodium cyanide mol ratio of contained yellow soda ash be 1: 1.15～1.25.
4, malonic ester preparation method as claimed in claim 1 is characterized in that: at weight percent content is to feed iS-One method prussic acid synthesis gas in 35～40% the aqueous sodium hydroxide solution to carry out building-up reactions, and temperature of reaction is controlled at 30～60 ℃; The content of sodium hydroxide is reached home less than the reaction of 0.8% back synthetic fluid sodium cyanide in the described reaction system; Then the liquid sodium cyanide that makes being added weight percent concentration is that 20～30% calcium chloride solution is handled, the usage quantity of wherein said calcium chloride solution: in the calcium chloride solution in calcium chloride and the liquid sodium cyanide mol ratio of contained yellow soda ash be 1: 1.0～1.4, make yellow soda ash and sodium hydroxide reaction in calcium chloride and the liquid sodium cyanide generate precipitation of calcium carbonate and calcium hydroxide precipitation, join with the Mono Chloro Acetic Acid is that raw material is through in the cyanogenation after the neutralization reaction again, cyanogenation finishes, cooling is below 60 ℃, remove by filter wherein precipitation of calcium carbonate and the sedimentary mixture of calcium hydroxide after carry out acidification reaction again, the dehydration and esterification obtain malonic ester.
5, malonic ester preparation method as claimed in claim 4, it is characterized in that: described the liquid sodium cyanide that makes is added weight percent concentration is that 20～30% calcium chloride solution is handled, wherein the usage quantity of calcium chloride solution is: in the calcium chloride solution in calcium chloride and the liquid sodium cyanide mol ratio of contained yellow soda ash be 1: 1.15～1.25, make yellow soda ash and sodium hydroxide reaction in calcium chloride and the liquid sodium cyanide generate precipitation of calcium carbonate and calcium hydroxide post precipitation, after removing by filter precipitation of calcium carbonate and calcium hydroxide precipitation mixture wherein earlier, join with the Mono Chloro Acetic Acid is raw material again, in the cyanogenation after the neutralization reaction, cyanogenation finishes and carries out acidification reaction again, and dehydration and esterification obtain malonic ester.
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| CNB2006100542547A CN100516016C (en) | 2006-04-29 | 2006-04-29 | Process for the preparation of malonic ester |
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| CNB2006100542547A CN100516016C (en) | 2006-04-29 | 2006-04-29 | Process for the preparation of malonic ester |
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| CN100516016C true CN100516016C (en) | 2009-07-22 |
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| CN101525290B (en) * | 2009-04-28 | 2012-06-13 | 安徽金邦医药化工有限公司 | Preparation method of diethyl malonate |
| CN111484039A (en) * | 2020-03-24 | 2020-08-04 | 营口德瑞化工有限公司 | Method for removing sodium/potassium carbonate and sodium/potassium hydroxide in sodium cyanide/potassium solution |
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