CN1323994C - Process for recovering methylene dichloride from multi-component mixed solution containing methylene dichloride - Google Patents
Process for recovering methylene dichloride from multi-component mixed solution containing methylene dichloride Download PDFInfo
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- CN1323994C CN1323994C CNB2005100264335A CN200510026433A CN1323994C CN 1323994 C CN1323994 C CN 1323994C CN B2005100264335 A CNB2005100264335 A CN B2005100264335A CN 200510026433 A CN200510026433 A CN 200510026433A CN 1323994 C CN1323994 C CN 1323994C
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- methylene dichloride
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- methylene chloride
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Abstract
The present invention relates to a method for recovering methylene chloride from multielement mixed liquor which contains methylene chloride, methanol, pyridinium, triethylamine and water. The present invention comprises the following main steps: two-step extraction and ordinary pressure batch fractionating under the condition of a variable reflux ratio. The present invention overcomes the defects of lower purity and low recovery rate of methylene chloride and high recovery cost of recovering methylene chloride from mixed liquor which contains methylene chloride, methanol, pyridinium, triethylamine and water of the prior art. The purity of methylene chloride which is recovered by the method of the present invention is not lower than 99.8 wt%, and the average recovery rate of the methylene chloride reaches 93%.
Description
Technical field
The present invention relates to a kind of recovery method of methylene dichloride, particularly a kind of method that from the multi-kinds mixtures liquid that comprises methylene dichloride, methyl alcohol, pyridine, triethylamine and water, reclaims methylene dichloride.
Background technology
The at present reported method that reclaims methylene dichloride from the multi-kinds mixtures liquid that contains methylene dichloride mainly is divided three classes: the first: extraction fractional distillation (abbreviation single stage method), as people such as Swiss Patent CH 605494 and Ke Lingjin at the test of methylene dichloride " from the ternary mixture reclaim " (Chinese Journal of Pharmaceuticals, 2002,33 (8), method 372-373), wherein the mixed solution among the patent CH 605494 consists of: methylene dichloride-trichloromethane-methyl alcohol, and adopting water is the extraction agent of extracting rectifying; Document " reclaiming the test of methylene dichloride from ternary mixed solvent " mixed solution consists of: methylene chloride-methanol-water, and adopting the Potassium ethanoate ethylene glycol solution is the extraction agent of extracting rectifying; It two is: the multi-kinds mixtures liquid that contains methylene dichloride is carried out rectifying earlier, carry out the method (abbreviation two-step approach) of adsorbing and removing moisture then, as people such as Wang Lixue at " application of 4A type molecular sieve in methylene dichloride reclaim to be produced " (Heilungkiang medicine, 2001,14 (3), institute's reported method 190-191), wherein said mixed solution consists of: methylene dichloride-water, the employing molecular sieve is a sorbent material; It three is: the multi-kinds mixtures liquid that will contain methylene dichloride earlier carries out rectifying, extraction then, carrying out two step rectifying at last again (is called for short: multistep processes), as Timofeev, V.S. wait the people at " Regeneration of methylene chloride and methanol formed duringantibiotic production " (Khim.-Farm.Zh., 17 (11), 1343-8 (Russian) 1983) and Shalygin, V.A. wait the people at " Regeneration of amethyiene chloride-methanol-acetone-waterindustrial mixture " (Tr.Inst.-Mosk.Khim.-Tekhnol.Inst.im.D.I.Mendeleeva, 156,119-23 (Russian) 1989.) institute's reported method in, Timofeev wherein, V.S. wait the mixed solution that relates in the described method of people to consist of: methylene chloride-methanol-butyl ethylacetic acid-water, extraction agent are water; And Shalygin relates to mixed solution in the described method of people such as V.A. and consists of: methylene chloride-methanol-acetone-water, extraction agent are water.
The technical issues that need to address of the present invention are: reclaim methylene dichloride from the multi-kinds mixtures liquid of being made up of methylene dichloride, methyl alcohol, pyridine, triethylamine and water (deriving from antibiotic production line waste liquid).When adopting prior art (, two or multistep processes) from the multi-kinds mixtures liquid of being made up of methylene dichloride, methyl alcohol, pyridine, triethylamine and water during the recovery methylene dichloride, its effect is undesirable.Therefore need the new methylene dichloride absorption method of research and development.
Summary of the invention
The object of the invention is, a kind of method that reclaims methylene dichloride from the multi-kinds mixtures liquid (deriving from antibiotic production line waste liquid) that comprises methylene dichloride, methyl alcohol, pyridine, triethylamine and water is provided.
The present inventor is through extensive and deep research, proposes the methylene dichloride recovery method of a kind of " low-temperature extraction removes impurity, varying reflux ratio batch fractionating purifying methylene dichloride stage by stage ", specifically comprises the steps:
(1) adding extraction agent A under 2～10 ℃ in the mixed solution that contains methylene dichloride, methyl alcohol, pyridine, triethylamine and water, extraction agent A add-on is 0.1～0.3 times of mixeding liquid volume; Under agitation condition, extract, tell extracting phase after leaving standstill;
(2) will by step (1) gained extracting phase with extraction agent B set by step the condition of (1) carry out reextraction, tell extracting phase;
(3) will carry out atmospheric pressure batch fractionating by step (2) gained extracting phase: at first adopt total reflux operation, this moment, the phegma phase-splitting water trap of need flowing through removed moisture and water-soluble impurity, and the total reflux time is 1.5～3.0h; Be (6～2) in reflux ratio then: collect middle runnings under 1 the condition, when the rectifying tower top temperature reaches 39.2 ℃, stop the collection of middle runnings; Be condition under to collect methylene dichloride at 1: 1 in reflux ratio at last, when the rectifying tower top temperature reaches 42.5 ℃, stop rectifying;
Wherein: said extraction agent A is that concentration is the inorganic acid aqueous solution of 0.05%～0.5wt%, and preferred concentration is 0.05%～0.5wt% hydrochloric acid, sulfuric acid or aqueous nitric acid; Said extraction agent B is the inorganic salt solution of 0.1%～0.3wt%, and preferred concentration is 0.1%～0.3wt% sodium salt, sylvite or calcium saline solution, and the best is NaCl, the CaCl of 0.1%～0.3wt% for concentration
2Or Na
2SO
4The aqueous solution.
For improving the rate of recovery of methylene dichloride better, the middle runnings that gets in the technique scheme step (3) can be recycled, that is: described middle runnings is incorporated into the extracting phase that obtains by step (1), then repeating step (2) and step (3).
Characteristics of the present invention are: carry out two step extractions earlier, then under the varying reflux ratio condition, carry out atmospheric pressure batch fractionating.The purity of the methylene dichloride of the recovery of existence when adopting prior art that the mixed solution that contains methylene dichloride, methyl alcohol, pyridine, triethylamine and water is carried out the methylene dichloride recovery and the defective that the rate of recovery is lower and cost recovery is high have been overcome.Adopt the method for the invention to reclaim and obtain methylene dichloride, its purity 〉=99.8wt%, the average recovery rate of methylene dichloride reaches 93%.
Embodiment
The recovery method of the said methylene dichloride of the present invention comprises the steps:
(1) be the inorganic acid aqueous solution of 0.05%～0.5wt% adding concentration under 2～10 ℃ in the mixed solution that contains methylene dichloride, methyl alcohol, pyridine, triethylamine and water, the add-on of inorganic acid aqueous solution is 0.1～0.3 times of mixeding liquid volume; Under agitation condition, extract, tell extracting phase after leaving standstill;
(2) will by step (1) gained extracting phase with the inorganic salt solution of 0.1%～0.3wt% set by step the condition of (1) carry out reextraction, tell extracting phase;
(3) will carry out atmospheric pressure batch fractionating by step (2) gained extracting phase: at first adopt total reflux operation, this moment, the phegma phase-splitting water trap of need flowing through removed moisture and water-soluble impurity, and the total reflux time is 1.5～3.0h; Be (6～2) in reflux ratio then: collect middle runnings under 1 the condition, when the rectifying tower top temperature reaches 39.2 ℃, stop the collection of middle runnings, the extracting phase that the middle runnings of gained is incorporated into by step (1) gained recycles; Be condition under to collect methylene dichloride at 1: 1 in reflux ratio at last, when the rectifying tower top temperature reaches 42.5 ℃, stop rectifying.
For better understanding the present invention, the invention will be further described below by embodiment, but for embodiment do not limit protection scope of the present invention:
Embodiment 1
(certain pharmacy provides to add the 1200L mixed solution in the glass-lined kettle, it contains 87.5%～92.8wt% methylene dichloride, 3.39%～7.89wt% methyl alcohol, 1.1%～2.2wt% pyridine, the water of 0.9%～1.9wt% triethylamine and 0.51wt%), with 120L concentration be the hydrochloric acid of 0.08wt%, stirred 20 minutes down at 10 ℃, remove water after leaving standstill; Adding 160L concentration again in still is the NaCl aqueous solution of 0.3wt%, stirs 20 minutes down at 10 ℃, leaves standstill and removes water; To add batch fractionating Tata still through the mixed solution (extracting phase) after the extraction and carry out rectifying: at first total reflux was closed phase-splitting water trap loop after (removing in the phase-splitting water trap at water and water-soluble impurity) in 2 hours in this process; Condition under begin collect middle runnings at 6: 1 in reflux ratio then, when reaching 39.2 ℃, the rectifying tower top temperature stops the collection of middle runnings, gained middle runnings 120L, concentration dichloromethane is 97.9wt% (extracting phase of incorporating into behind hcl as extraction agent recycles); In reflux ratio condition bottom discharge in 1: 1, when the rectifying tower top temperature reaches 42.5 ℃, stop rectifying at last, collect methylene dichloride 900L, concentration is 99.85wt%, methylene dichloride total recovery 92.5wt%.
Embodiment 2
Adding 2000L mixed solution (source and form with embodiment 1) and 600L concentration in the glass-lined kettle is the sulfuric acid of 0.1wt%, 5 ℃ of stirrings 25 minutes down, leaves standstill the branch phase of anhydrating; Adding 300L concentration again in still is the CaCl of 0.1wt%
2The aqueous solution stirred 20 minutes down at 5 ℃, left standstill the branch phase of anhydrating; To add batch fractionating Tata still through the mixed solution (extracting phase) after the extraction and carry out rectifying: at first total reflux was closed phase-splitting water trap loop after (removing in the phase-splitting water trap at water and water-soluble impurity) in 2.5 hours in this process; Condition under begin collect middle runnings at 6: 1 in reflux ratio then, when reaching 39.2 ℃, the rectifying tower top temperature stops the collection of middle runnings, gained middle runnings 250L, concentration dichloromethane is 98.2wt% (extracting phase of incorporating into after the sulfuric acid extraction recycles); In reflux ratio condition bottom discharge in 1: 1, when tower top temperature reaches 42.5 ℃, stop rectifying, collect methylene dichloride 1390L, concentration is 99.92wt%, methylene dichloride total recovery 93.1%.
Embodiment 3
Adding 2000L mixed solution (source and form with embodiment 1) and 380L concentration in the glass-lined kettle is the nitric acid of 0.1wt%, 2 ℃ of stirrings 25 minutes down, leaves standstill the branch phase of anhydrating; Adding 200L concentration again in still is the Na of 0.3wt%
2SO
4The aqueous solution stirred 20 minutes down at 3 ℃, the static branch phase of anhydrating; To add batch fractionating Tata still through the mixed solution (extracting phase) after the extraction and carry out rectifying: at first total reflux was closed phase-splitting water trap loop after (removing in the phase-splitting water trap at water and water-soluble impurity) in 3.0 hours in this process; Condition under begin collect middle runnings at 2: 1 in reflux ratio then, when reaching 39.2 ℃, the rectifying tower top temperature stops the collection of middle runnings, gained middle runnings 530L, concentration dichloromethane is 98.90wt% (extracting phase of incorporating into after the nitric acid extraction recycles); In reflux ratio condition bottom discharge in 1: 1, when tower top temperature reaches 42.5 ℃, stop rectifying, collect methylene dichloride 1170L, concentration is 99.93wt%, methylene dichloride total recovery 93.2%.
Claims (5)
1, a kind of recovery method of methylene dichloride, it comprises the steps:
(1) adding extraction agent A under 2～10 ℃ in the mixed solution that contains methylene dichloride, methyl alcohol, pyridine, triethylamine and water, extraction agent A add-on is 0.1～0.3 times of mixeding liquid volume; Under agitation condition, extract, tell extracting phase after leaving standstill;
(2) will by step (1) gained extracting phase with extraction agent B set by step the condition of (1) carry out reextraction, tell extracting phase;
(3) will carry out atmospheric pressure batch fractionating by step (2) gained extracting phase: at first adopt total reflux operation, this moment, the phegma phase-splitting water trap of need flowing through removed moisture and water-soluble impurity, and the total reflux time is 1.5～3.0 hours; Be (6～2) in reflux ratio then: collect middle runnings under 1 the condition, when the rectifying tower top temperature reaches 39.2 ℃, stop the collection of middle runnings; Be condition under to collect methylene dichloride at 1: 1 in reflux ratio at last, when the rectifying tower top temperature reaches 42.5 ℃, stop rectifying;
Wherein: said extraction agent A is that concentration is the inorganic acid aqueous solution of 0.05%～0.5wt%, and said extraction agent B is the inorganic salt solution of 0.1%～0.3wt%.
2, recovery method as claimed in claim 1 is characterized in that, wherein said inorganic acid aqueous solution is hydrochloric acid, sulfuric acid or aqueous nitric acid.
3, recovery method as claimed in claim 1 is characterized in that, wherein said inorganic salt solution is sodium salt, sylvite or calcium saline solution.
4, recovery method as claimed in claim 3 is characterized in that, wherein said inorganic salt solution is NaCl, CaCl
2Or Na
2SO
4The aqueous solution.
5, as described any one recovery method of claim 1～4, it is characterized in that, wherein in the step (3) the extracting phase incorporated into by step (1) gained of middle runnings recycle, that is: described middle runnings is incorporated into the extracting phase that obtains by step (1), repeating step (2) and step (3) then.
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| CNB2005100264335A CN1323994C (en) | 2005-06-03 | 2005-06-03 | Process for recovering methylene dichloride from multi-component mixed solution containing methylene dichloride |
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| CNB2005100264335A CN1323994C (en) | 2005-06-03 | 2005-06-03 | Process for recovering methylene dichloride from multi-component mixed solution containing methylene dichloride |
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| CN1323994C true CN1323994C (en) | 2007-07-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103185970B (en) * | 2011-12-29 | 2016-05-25 | 林先锋 | The optical routing method and apparatus of translation polarised light, control optical signal, selection wavelength |
| CN104086355B (en) * | 2014-07-14 | 2015-07-29 | 河北工业大学 | A kind of method of separate dichloromethane, triethylamine and water |
| CN105523889B (en) * | 2016-01-17 | 2017-12-08 | 济南大学 | A kind of tert-butyl alcohol triethylamine azeotropic mixture extraction rectifying method |
| CN110256200A (en) * | 2019-07-08 | 2019-09-20 | 新中天环保股份有限公司 | A method of separating and recovering solvent from pharmacy class methanol mixing solvent slop |
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Non-Patent Citations (5)
| Title |
|---|
| 从三元混合溶剂中回收二氯甲烷的试验 柯凌进等，中国医药工业杂志，第33卷第8期 2002 * |
| 从三元混合溶剂中回收二氯甲烷的试验 柯凌进等，中国医药工业杂志，第33卷第8期 2002;加盐萃取分离吡啶水混合物 田庆来等，河北化工，第2卷 2002;磷酸喷淋吸收法处理三乙胺废气 顾敏，环境导报，第9卷 2003;头孢拉定生产中的废溶媒的回收 张文林等，中国抗生素杂志，第29卷第6期 2004 * |
| 加盐萃取分离吡啶水混合物 田庆来等，河北化工，第2卷 2002 * |
| 头孢拉定生产中的废溶媒的回收 张文林等，中国抗生素杂志，第29卷第6期 2004 * |
| 磷酸喷淋吸收法处理三乙胺废气 顾敏，环境导报，第9卷 2003 * |
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