CN1382671A - Process for preparing ester from acetic acid and chlorine gas by cyanation in advance - Google Patents
Process for preparing ester from acetic acid and chlorine gas by cyanation in advance Download PDFInfo
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- CN1382671A CN1382671A CN 01107983 CN01107983A CN1382671A CN 1382671 A CN1382671 A CN 1382671A CN 01107983 CN01107983 CN 01107983 CN 01107983 A CN01107983 A CN 01107983A CN 1382671 A CN1382671 A CN 1382671A
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- acetic acid
- ester
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- cyanoacetate
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Abstract
A process for preparing ester (malonate or cyanoacetate) from acetic acid and chlorine gas includes chlorination reaction, adding water, neutralizing reaction, cyanating reaction at 100-1150 deg.C, esterifying reaction and distilling. Its advantages are low cost and simple process.
Description
The present invention relates to acetic acid and chlorine is that the raw material pre-cyanation is produced the technology, particularly malonic ester of ester and the production technique of cyanoacetate.
Pre-cyanation prepares malonic ester, cyanoacetate, prior art processes is: be starting raw material with acetic acid, acetic acid carries out chlorination reaction under catalyzer (sulphur or aceticanhydride) effect, stop chlorination reaction when solid-liquid ratio weighs 1.363～1.365/80 ℃, then the chlorination work in-process that obtain are carried out crystallization, centrifugal treating.Its concrete operations are: the chlorination work in-process are pressed into stirred pot, add crystal seed and be incubated 6～8 hours between 50～60 ℃, material is put into the suction filtration jar took out chlorine 4～5 hours, with the centrifugal Mono Chloro Acetic Acid finished product that obtains of Mono Chloro Acetic Acid crystallization, be grilled in the pail pack.Pour Mono Chloro Acetic Acid into neutralization tank, with in the yellow soda ash and PH between 7～7.5, neutralization finishes material is pressed into the cyaniding jar, the throw liq sodium cyanide carries out cyaniding, insulation more than 100 ℃ 30 minutes, insulation finishes and material is pulled to esterification reaction tank drops into alcohol carry out esterification under the catalyst sulfuric acid effect, drop into then retort distill finished product.Malonic ester and cyanoacetate are to determine that in Esterification Stage generation is malonic ester or cyanoacetate.The weak point of this technology is after the chlorination reaction again through crystallization, centrifugal, long flow path, crystallization, centrifugal, in and the process operations environment poor, labour intensity is big, the production cost height.
The purpose of this invention is to provide a kind of improved be the technology that the raw material pre-cyanation is produced ester with acetic acid and chlorine, simplify working process, improve production environment, reduce labour intensity and production cost.
Of the present invention is the technology of raw material production ester with acetic acid and chlorine, obtain finished product through chlorination reaction, neutralization reaction, cyanogenation, esterification, distillation, it is characterized in that directly carrying out neutralization reaction after chlorination work in-process that acetic acid and catalyzer carry out obtaining after the chlorination reaction add water, the weight ratio of acetic acid and water is 1: 0.75～0.90, is 1: 2.50～3.00 in molar ratio.
The present invention has omitted after the chlorination reaction the half-finished processing of chlorination, throws except crystallization, rotary process.The same prior art of other manufacturing condition, but after the neutralization reaction, the pH value of material is preferably 6～7; The temperature of cyanogenation preferably is controlled to be 100～115 ℃.By the improvement of these processing parameters, under the situation that does not influence quality product, can improve work situation, reduce labour intensity and production cost, shorten the production cycle.
Because the present invention does not change Esterification Stage, so the present invention is suitable for the production of malonic ester and cyanoacetate.
Described malonic ester is the compound of following general formula:
CH
2(COOR)
2R=C wherein
nH
2n+11≤n≤4.Comprise isomers.
But malonic ester of the present invention is preferably diethyl malonate, dimethyl malonate.
Described cyanoacetate is the compound of following general formula:
CNCH
2COOR is R=C wherein
nH
2n+11≤n≤8.Comprise isomers.
Cyanoacetate is preferably ethyl cyanoacetate, methyl cyanoacetate.
The technology that the present invention is complete is: acetic acid is pressed into the chlorination jar, adding catalyzer (sulphur or aceticanhydride) heats up, logical chlorine when temperature rises to 70 ℃, when catalyzer is sulphur, temperature is remained between 80～95 ℃, when catalyzer is aceticanhydride, temperature is remained between 90～105 ℃, stop logical chlorine 1.360～1.365/80 ℃ the time when solid-liquid ratio weighs, in the chlorination work in-process, add water, under agitation condition, feed liquid is neutralized to PH=6～7 with aqueous sodium carbonate.Liquid cyanogen suction cyaniding jar is started stirring, simultaneously will in the feed liquid of becoming reconciled be pressed into the cyaniding jar, the control reaction conditions heats up the reaction nature, insulation is 30 minutes between 100～110 ℃, be cooled to and obtain the cyanoacetic acid sodium solution below 40 ℃, cyanoacetic acid sodium is obtained cyanoacetic acid solution with hcl acidifying.Handle then and carry out esterification.
For malonic ester: cyanoacetic acid solution is cooled to below 50 ℃ behind decompression dehydration, directly adds industrial alcohol (95% ethanol, volume ratio), in about 75 ℃, drip the vitriol oil then, finish, 80～100 ℃ of reactions 3 hours, reaction is cooled to the inorganic salt that are dissolved in water below 70 ℃ after finishing, leave standstill, tell upper strata liquid, be neutralized to PH=7～8 with sodium carbonate solution, adjust vacuum and between 0.096～0.098Mpa, carry out underpressure distillation, obtain diethyl malonate.Same other malonic ester product adds correspondent alcohol and gets final product by this esterification.Different alcohol is distinguished to some extent in the Esterification Stage temperature of reaction, as 70～90 ℃ of methyl alcohol, and 80～105 ℃ of propyl alcohol, 90～120 ℃ in butanols.
In molar ratio: acetic acid: 1
Catalyzer sulphur: 0.033～0.071; Catalyzer aceticanhydride: 0.116
Water: 2.50～3.00
Liquid sodium cyanide: 0.85～0.87
Hydrochloric acid: 0.96～1.04
Sulfuric acid: 1.32～1.41
Alcohol: 2.05～2.22
By weight, acetic acid: 1
Sulphur: 0.018～0.038; Aceticanhydride: 0.2
Water: 0.75～0.90
Liquid sodium cyanide: 0.702～0.711
Hydrochloric acid: 0.590～0.634
Sulfuric acid: 2.170～2.311
Industrial alcohol: 1.571～1.702, methyl alcohol 1.093～1.185, propyl alcohol 2.050～2.220, butanols 2.528～2.739, or the like
Wherein liquid sodium cyanide (30%), hydrochloric acid (31%) have been pure amount.
For cyanoacetate: (0.090～0.098Mpa) is not more than 15% to water content to the dehydration of cyanoacetic acid solution decompression at 80～100 ℃, be cooled to 50～60 ℃ then, add dehydrated alcohol, the sodium-chlor that filtering generates gets filtrate, add the vitriol oil in 80～100 ℃ of insulations 5 hours, dealcoholysis.Be cooled to after dealcoholysis finishes and add the pure and mild vitriol oil below 50 ℃, 80～100 ℃ of insulations 5 hours, the secondary dealcoholysis, dealcoholysis finishes and adds the pure and mild vitriol oil, and 80～100 ℃ of insulations 4 hours, three dealcoholysis finished and add water, be neutralized to PH=7～8 with saturated sodium carbonate solution, static 1 hour, divide the sub-cloud buck, suction filtration gets thick ester.With thick ester material the decompression (distill under the vacuum 0.095～0.098MPa) ethyl cyanoacetate.Same other cyanoacetate product adds correspondent alcohol and gets final product by this esterification.Different alcohol is distinguished to some extent in the Esterification Stage temperature of reaction, as 70～90 ℃ of methyl alcohol, and 80～105 ℃ of propyl alcohol, 90～120 ℃ in butanols, 90～120 ℃ of octanols.
In molar ratio, acetic acid: 1
Sulphur: 0.033～0.071, aceticanhydride: 0.058～0.116
Water: 2.50～3.00
Liquid sodium cyanide: 0.85～0.87
Hydrochloric acid: 0.96～1.04
Sulfuric acid: 0.061～0.074
Alcohol: 3.184～3.397
By weight, acetic acid: 1
Sulphur: 0.018～0.038; Aceticanhydride 0.1～0.2
Water: 0.75～0.90
Liquid sodium cyanide: 0.702～0.711
Hydrochloric acid: 0.590～0.634
Sulfuric acid: 0.10～0.12
Dehydrated alcohol: 2.446～2.609, methyl alcohol 1.698～1.812, butanols 3.927～4.191, octanol 6.90～7.37, or the like.
Liquid sodium cyanide (30%), hydrochloric acid (31%) have been pure amount.
Advantage of the present invention: simplified technical process, improved production environment, reduced labour intensity and production cost, shortened the production cycle.
Following examples one～embodiment eight is the embodiment of malonic ester.
Embodiment one:
Acetic acid: 233kg, sulphur: 7kg, water: 184kg, liquid sodium cyanide: 549kg, hydrochloric acid: 400kg, sulfuric acid: 530kg, industrial alcohol 397kg
Liquid sodium cyanide (30%), hydrochloric acid (31%) are by pure.
Acetic acid is pressed into the chlorination jar, adds sulphur and heat up, logical chlorine when temperature rises to 70 ℃ increases logical chlorine dose in the time of 80 ℃, stops logical chlorine when solid-liquid ratio weighs 1.362/80 ℃ the time, obtains chlorination work in-process (sample 1).In the chlorination work in-process, add water (sample 2), under agitation condition, feed liquid is neutralized to PH=6.5 with aqueous sodium carbonate.Liquid cyanogen suction cyaniding jar is started stirring, the feed liquid of becoming reconciled in inciting somebody to action simultaneously is pressed into the cyaniding jar, the control reaction conditions heats up the reaction nature, get cyanoacetic acid sodium solution (sample 3) after 30 minutes in insulation between 100～110 ℃, throw hydrochloric acid and open the vapour decompression dehydration, cooling when the liquid temperature reaches 100 ℃, add industrial alcohol, in about 75 ℃, drip the vitriol oil then, finish, 80～100 ℃ of reactions 3 hours, be cooled to after reaction finishes and add 1000kg water dissolution inorganic salt below 70 ℃, leave standstill, tell upper strata liquid, be neutralized to PH=7 with saturated sodium carbonate solution and obtain thick ester, thick ester is pulled to retort, adjust vacuum and carry out underpressure distillation, when steam temperature drops to 95 ℃ again, distill when material no longer goes out by finish (sample 5) at 0.098Mpa.
Sample 1 sample 2 Monochloro Acetic Acid % 91.11 68.38 dichloro acetic acid % 6.77 4.85 acyl chlorides % 1.35 0.43
Sample 3 cyanogen root % 0.14 cyanoacetic acid sodium % 27.72
Sample 4 samples 5 contrast (prior art processes) diethyl malonate % 98.58 99.40 99.41 dichloro acetic acid ester % 0.08 0.05 0.06
Embodiment two:
With embodiment one technology, in molar ratio,
Acetic acid: 1
Sulphur: 0.033
Water: 2.8
Liquid sodium cyanide: 0.85
Hydrochloric acid: 0.96
Sulfuric acid: 1.32
Industrial alcohol: 2.05
Wherein liquid sodium cyanide (30%), hydrochloric acid (31%) have been pure amount.
Embodiment three:
Technology is with embodiment one, in molar ratio,
Acetic acid: 1
Sulphur: 0.056
Water: 2.50
Liquid sodium cyanide: 0.86
Hydrochloric acid: 0.98
Sulfuric acid: 1.38
Industrial alcohol: 2.15
Embodiment four:
Technology is with embodiment one, in molar ratio,
Acetic acid: 1
Aceticanhydride: 0.116
Water: 3.00
Liquid sodium cyanide: 0.87
Hydrochloric acid: 1.04
Sulfuric acid: 1.41
Industrial alcohol: 2.22
Embodiment five:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Aceticanhydride: 0.116
Water: 2.56
Liquid sodium cyanide: 0.85
Hydrochloric acid: 0.99
Sulfuric acid: 1.40
Methyl alcohol: 2.10
Embodiment six:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Aceticanhydride: 0.116
Water: 3.00
Liquid sodium cyanide: 0.87
Hydrochloric acid: 1.04
Sulfuric acid: 1.41
N-propyl alcohol: 2.22
Embodiment seven:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Sulphur: 0.048
Water: 2.70
Liquid sodium cyanide: 0.87
Hydrochloric acid: 0.96
Sulfuric acid: 1.34
Propyl carbinol: 2.10
Embodiment eight:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Sulphur: 0.116
Water: 3.00
Liquid sodium cyanide: 0.87
Hydrochloric acid: 1.04
Sulfuric acid: 1.41
Isopropylcarbinol: 2.00
Following examples nine～embodiment 17 is cyanoacetate embodiment
Embodiment nine:
Acetic acid: 184kg, sulphur: 6kg, water: 150kg, 30% liquid sodium cyanide: 432kg, 31% hydrochloric acid: 364kg, sulfuric acid: 20kg, dehydrated alcohol 460kg
Acetic acid is pressed into the chlorination jar, adds sulphur and heat up, logical chlorine when temperature rises to 70 ℃ increases logical chlorine dose in the time of 80 ℃, stops logical chlorine when solid-liquid ratio weighs 1.365/80 ℃ the time, obtains chlorination work in-process (sample 1).In the chlorination work in-process, add water (sample 2), under agitation condition, feed liquid is neutralized to PH=6.5 with aqueous sodium carbonate.Liquid cyanogen suction cyaniding jar is started stirring, the feed liquid of becoming reconciled in inciting somebody to action simultaneously is pressed into the cyaniding jar, the control reaction conditions heats up the reaction nature, be cooled to 37 ℃ after 30 minutes in insulation between 100～110 ℃ and get cyanoacetic acid sodium solution (sample 3), throw hydrochloric acid and open the vapour decompression dehydration, when the liquid temperature reaches 94 ℃, dehydration did not finish when water base of vacuum 0.098Mpa did not go out.Be cooled to 56 ℃, add 230kg ethanol, the sodium-chlor that filtering generates gets filtrate, adds the 10kg vitriol oil, in 80～100 ℃ of insulations 4 hours, three dealcoholysis.Dealcoholysis finishes and adds water, be neutralized to PH=8 with saturated sodium carbonate solution, static 1 hour, divide the sub-cloud buck, suction filtration gets thick ester, and thick ester material is distilled down in decompression (vacuum 0.098Mpa), when steam temperature rises to 31 ℃, go out to hang down and boil, the back continuation that gone out to hang down to boil refluxes, and sampling is surveyed when diethyl malonate content is 0.22% (sample 4) in the material and begun finished product, and steam temperature rises to 125 ℃ at this moment; When steam temperature was reduced to below 80 ℃, when material did not go out substantially, distillation finished, and got finished product (sample 5).
Sample 1 sample 2 Monochloro Acetic Acid % 87.90 60.65 dichloro acetic acid % 7.07 4.88 acyl chlorides % 1.93 0.38
Sample 3 cyanogen root % 0.23 cyanoacetic acid sodium % 27.06
Sample 4 samples 5 contrast (prior art processes) ethyl cyanoacetate % 99.32 99.41 99.40 diethyl malonate % 0.22 0.37 0.36
Embodiment ten:
Technology is with embodiment nine, in molar ratio,
Acetic acid: 1
Sulphur: 0.033
Water: 2.50
Liquid sodium cyanide: 0.85
Hydrochloric acid: 0.98
Sulfuric acid: 0.07
Dehydrated alcohol: 3.184
Liquid sodium cyanide (30%), hydrochloric acid (31%) have been pure amount.
Embodiment 11:
Technology is with embodiment nine, in molar ratio,
Acetic acid: 1
Sulphur: 0.058
Water: 3.00
Liquid sodium cyanide: 0.87
Hydrochloric acid: 0.96
Sulfuric acid: 0.061
Dehydrated alcohol: 3.255
Embodiment 12:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Sulphur: 0.071
Water: 2.56
Liquid sodium cyanide: 0.86
Hydrochloric acid: 0.98
Sulfuric acid: 0.07
Methyl alcohol: 3.184
Embodiment 13:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Sulphur: 0.068
Water: 2.57
Liquid sodium cyanide: 0.87
Hydrochloric acid: 1.04
Sulfuric acid: 0.074
Propyl carbinol: 3.388
Embodiment 14:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Aceticanhydride: 0.068
Water: 2.50
Liquid sodium cyanide: 0.85
Hydrochloric acid: 0.98
Sulfuric acid: 0.07
Octanol: 3.184
Embodiment 17:
Technology is with of the present invention, in molar ratio,
Acetic acid: 1
Aceticanhydride: 0.033
Water: 2.50
Liquid sodium cyanide: 0.85
Hydrochloric acid: 0.98
Sulfuric acid: 0.07
Hexanol: 3.184
Claims (7)
1, be the technology that the raw material pre-cyanation is produced ester with acetic acid and chlorine, obtain finished product through chlorination reaction, neutralization reaction, cyanogenation, esterification, distillation, it is characterized in that directly carrying out neutralization reaction after chlorination work in-process that acetic acid and catalyzer carry out obtaining after the chlorination reaction add water, the weight ratio of acetic acid and water is 1: 0.75～0.90.
2, technology according to claim 1, it is characterized in that neutralization reaction after, the pH value of material is 6～7.
3, technology according to claim 1, the temperature that it is characterized in that cyanogenation is 100～115 ℃.
4, technology according to claim 1 is characterized in that described ester is a malonic ester, has following general formula:
CH
2(COOR)
2R=C wherein
nH
2n+11≤n≤4.
5, technology according to claim 4 is characterized in that described malonic ester is a diethyl malonate.
6, technology according to claim 1 is characterized in that described ester is a cyanoacetate, has following general formula:
CNCH
2COOR is R=C wherein
nH
2n+11≤n≤8.
7, technology according to claim 6 is characterized in that described cyanoacetate is an ethyl cyanoacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011079835A CN1169784C (en) | 2001-04-26 | 2001-04-26 | Process for preparing ester from acetic acid and chlorine gas by cyanation in advance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011079835A CN1169784C (en) | 2001-04-26 | 2001-04-26 | Process for preparing ester from acetic acid and chlorine gas by cyanation in advance |
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| Publication Number | Publication Date |
|---|---|
| CN1382671A true CN1382671A (en) | 2002-12-04 |
| CN1169784C CN1169784C (en) | 2004-10-06 |
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ID=4656875
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011079835A Expired - Fee Related CN1169784C (en) | 2001-04-26 | 2001-04-26 | Process for preparing ester from acetic acid and chlorine gas by cyanation in advance |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424066C (en) * | 2006-04-20 | 2008-10-08 | 重庆紫光化工股份有限公司 | Process of preparing malonic ester |
| CN102633682A (en) * | 2012-03-20 | 2012-08-15 | 河北诚信有限责任公司 | Continuous production process of cyanoacetate |
-
2001
- 2001-04-26 CN CNB011079835A patent/CN1169784C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100424066C (en) * | 2006-04-20 | 2008-10-08 | 重庆紫光化工股份有限公司 | Process of preparing malonic ester |
| CN102633682A (en) * | 2012-03-20 | 2012-08-15 | 河北诚信有限责任公司 | Continuous production process of cyanoacetate |
| CN102633682B (en) * | 2012-03-20 | 2014-01-15 | 河北诚信有限责任公司 | Continuous production process of cyanoacetate |
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| Publication number | Publication date |
|---|---|
| CN1169784C (en) | 2004-10-06 |
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