CN102079712A - Method for recycling anhydrous organic amine from organic amine salt - Google Patents
Method for recycling anhydrous organic amine from organic amine salt Download PDFInfo
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- CN102079712A CN102079712A CN2010106190139A CN201010619013A CN102079712A CN 102079712 A CN102079712 A CN 102079712A CN 2010106190139 A CN2010106190139 A CN 2010106190139A CN 201010619013 A CN201010619013 A CN 201010619013A CN 102079712 A CN102079712 A CN 102079712A
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Abstract
The invention relates to a method for recycling an organic amine salt. The method for recycling anhydrous organic amine from an organic amine salt comprises the step of: with calcium oxide or a mixture containing more than 50 percent of calcium oxide as a raw material, reacting with the organic amine salt under stirring to recycle the anhydrous organic amine. The method is creatively characterized in that moisture is eliminated in situ without additional organic amine drying devices by using the alkalinity and water reactivity of the calcium oxide. Excessive calcium oxide in the reaction just reacts with generated water to play a role of drying the organic amine, the reaction and the drying are carried out simultaneously in the same reaction device, and the anhydrous organic amine can be recycled without other drying devices. If an organic solvent dispersing method is adopted, the organic amine with low boiling point is recycled, the organic solvent can be directly recycled through simple separation and can be repeatedly recycled without being subjected to any processing. The solid waste generated in the method is only inorganic salt and inorganic base which can be recycled, the method is safe and environmental-friendly and has low cost, and no wastewater is generated.
Description
Technical field
The present invention relates to chemical recovery method, particularly the recovery method of organic amine salt.
Background technology
Present known organic amine salt reclaims the organic amine method, substantially be to adopt dropping sodium or potassium hydroxide aqueous solution in the suspension liquid of the solid of organic amine salt or organic solvent, react the recovery organic amine, this method has many defectives: (1) equipment requirements may be complicated; (2) three wastes produce more; (3) amplifieroperation difficulty.Adopt the aqueous solution of mineral alkali to reclaim.Guarantee that the organic amine that reclaims is anhydrous, must add a cover drying plant in the still-process in addition, if guarantee the necessary higher alkali lye of working concentration of higher recovery, and high-concentration alkali liquor is easy to separate out solid in amplification process, and this scheme produces a large amount of waste water and useless solid two kinds of wastes; If take organic solvent to disperse reaction, though reduced the generation of waste water, the water that produces in the reaction process can cause the solid in the reaction solution to be bonded on the still wall, can't blowing in the amplification process, this scheme need add drying plant equally in addition and reduce the moisture of recovery organic amine, and cost recovery is too high
Summary of the invention
The objective of the invention is to overcome above-mentioned not enough problem, provide a kind of and reclaim the method for anhydrous organic amine from organic amine salt, method is simple, safety and environmental protection, low cost, the organic amine of recovery moisture low, yield is high.
The technical scheme that the present invention is taked for achieving the above object is: a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, adopting calcium oxide or calcium oxide content is raw material greater than 50% mixture, reclaims anhydrous organic amine with the organic amine salt stirring reaction.
Described calcium oxide or calcium oxide content, slowly heat up with after organic amine salt mixes fully greater than 50% mixture again, impel reaction to carry out; Also the suspension liquid of the organic solvent of one of them reactant can be heated to certain temperature, slowly add the another one reactant more in batches, come controls reaction speed by the control feed rate, when especially organic amine is lower boiling gas, needs the control response speed avoid gas to produce excessive velocities and cause dashing material or other dangerous accidents.
Described solid-liquid reaction mixture disperses with high boiling organic solvent, or organic amine, 20 ~ 105 ℃ of temperature of reaction are directly reclaimed in solid reaction.
The anhydrous organic amine of described recovery is lower boiling gas, then is recovered into special storage tank by condensation; Be lower boiling liquid, then by distillation (during solid-solid reaction) and solids constituent from, perhaps rectifying (during solid-liquid reaction) separates with dispersion solvent, and direct reuse is to next batch after filtering for the organic solvent of dispersion usefulness, and the solid after the reaction is inorganic salt and mineral alkali.
The strong acid salt of described organic amine is meant hydrochloride, vitriol, phosphoric acid salt, sulfonate, inorganic and organic acid such as trifluoroacetic acid; The mol ratio of described calcium oxide and organic amine salt hydrochlorate is 1.1 ~ 1.5:1; The mol ratio of calcium oxide and vitriol is 2.0 ~ 3.0:1; Calcium oxide and phosphatic mol ratio are 3.0 ~ 4.5:1.
Described calcium oxide content is the mixture of calcium oxide and alkali cpd greater than 50% mixture, and alkali cpd refers to sodium hydroxide or potassium hydroxide etc.
The organic amine of described recovery comprises a replacement at room temperature being gaseous state or liquid lower boiling organic amine, and two replace and trisubstituted organic amine.
Adopt in the described solid-liquid reaction high boiling organic solvent be not with the inertia alkane or the aromatic hydrocarbons of reaction raw materials and product generation chemical reaction, as toluene or heptane etc.
Reaction mechanism of the present invention following (is example with the dimethylamine hydrochloride):
2CaO+ 2DMA-HCl------〉2DMA+?CaCl
2 +?Ca（OH）
2
CaO?+?NaOH?+?DMA-HCl —————〉DMA?+?NaCl +Ca（OH）
2
Novelty key of the present invention is to utilize the alkalescence and the water reactivity of calcium oxide, and original position is eliminated moisture, need not other organic amine drying plant.Calcium oxide excessive in the reaction reacts with the water that generates just, plays the effect of dry organic amine, and reaction is carried out in same conversion unit simultaneously with dry, and need not other drying plants is the recyclable anhydrous organic amine that obtains.If take the organic solvent dispersing method, reclaim for lower boiling organic amine, but organic solvent process simple separation direct reuse, and repeatedly reuse repeatedly, need not any processing.The solid waste that the present invention produces only be inorganic salt and mineral alkali, can recycling, wherein there is not the waste water generation, and safety and environmental protection and cost are low.
Embodiment:
Embodiment 1
In a 500ml four-hole bottle that mechanical stirring, thermometer, reflux exchanger, distiller condenser and receiving bottle be housed, add 68.0g(1.2mol) solid oxidation calcium, 81.5g toluene and 81.5g(1.0mol) dimethylamine hydrochloride.Reflux exchanger feeds recirculated water, and distiller condenser feeds the heat-eliminating medium below-10 ℃, and receiving bottle is lowered the temperature with the heat-eliminating medium below-5 ℃.Slowly be warming up to 85 ℃ after open stirring, and 85 ℃ of insulations till do not have dimethylamine and flow out, reaction finishes.Collect the about 33.8g of dimethylamine, moisture＜0.2%, yield about 75%.
Embodiment 2
In a 500ml four-hole bottle that mechanical stirring, thermometer, distiller condenser and receiving bottle be housed, add 84.1g(1.5mol) solid oxidation calcium, 81.5g(1.0mol) dimethylamine hydrochloride.Distiller condenser feeds the heat-eliminating medium below-10 ℃, and receiving bottle is lowered the temperature with the heat-eliminating medium below-5 ℃.Slowly be warming up to 85 ℃ after open stirring, and 85 ℃ of insulations till do not have dimethylamine and flow out, reaction finishes.Collect the about 40.0g of dimethylamine, moisture＜0.2%, yield about 89%.
Embodiment 3
In a 500ml four-hole bottle that mechanical stirring, thermometer, rectifying column, distiller condenser and receiving bottle be housed, add.68.0g(1.2mol) solid oxidation calcium, 81.5g toluene and 85.6g(0.5mol) diethylamine vitriol, condenser feeds the heat-eliminating medium below 0 ℃.Open to stir slowly intensification rectifying of back, still temperature rise to 95 ℃ insulation is not till have diethylamine and flow out, and reaction finishes.Collect the about 29.3g of diethylamine, moisture＜0.2%, yield about 80%.
Embodiment 4
In a 500ml rectifier unit that mechanical stirring, thermometer be housed, add 34.0g(0.6mol) solid oxidation calcium, 81.5g toluene and 68.8g(0.5mol) triethylamine hydrochloride.Open to stir slowly intensification rectifying triethylamine of back, still temperature rise to 100 ℃ insulation is not till have triethylamine and flow out, and reaction finishes.Collect the about 45.5g of triethylamine, moisture＜0.2%, yield about 90%.
Claims (9)
1. one kind is reclaimed the method for anhydrous organic amine from organic amine salt, it is characterized in that: adopting calcium oxide or calcium oxide content is raw material greater than 50% mixture, reclaims anhydrous organic amine with the organic amine salt stirring reaction.
2. according to claim 1ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: calcium oxide or calcium oxide content, slowly heat up with after organic amine salt mixes fully greater than 50% mixture again, impel reaction to carry out; Or the suspension liquid of the organic solvent of one of them reactant is heated to certain temperature, slowly add the another one reactant more in batches, come controls reaction speed by the control feed rate, when especially organic amine is lower boiling gas, needs the control response speed avoid gas to produce excessive velocities and cause dashing material or other dangerous accidents.
3. according to claim 1 and 2ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: the solid-liquid reaction mixture disperses with high boiling organic solvent, or the direct recovery organic amine of solid reaction, 20 ~ 105 ℃ of temperature of reaction.
4. according to claim 1 and 2ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: the anhydrous organic amine of recovery is lower boiling gas, then is recovered into special storage tank by condensation; Be lower boiling liquid, then by distillation (during solid-solid reaction) and solids constituent from, perhaps rectifying (during solid-liquid reaction) separates with dispersion solvent, and direct reuse is to next batch after filtering for the organic solvent of dispersion usefulness, and the solid after the reaction is inorganic salt and mineral alkali.
5. according to claim 1 and 2ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: the strong acid salt of organic amine is meant inorganic and organic acids such as organic amine salt hydrochlorate, vitriol, phosphoric acid salt, sulfonate or trifluoroacetic acid.
6. according to claim 5ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: the mol ratio of described calcium oxide and organic amine salt hydrochlorate is 1.1 ~ 1.5:1; The mol ratio of calcium oxide and vitriol is 2.0 ~ 3.0:1; Calcium oxide and phosphatic mol ratio are 3.0 ~ 4.5:1.
7. according to claim 1 and 2ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: calcium oxide content is the mixture of calcium oxide and alkali cpd greater than 50% mixture, and alkali cpd refers to sodium hydroxide or potassium hydroxide etc.
8. according to claim 1 and 2ly a kind ofly reclaim the method for anhydrous organic amine from organic amine salt, it is characterized in that: the organic amine of described recovery comprises a replacement at room temperature being gaseous state or liquid lower boiling organic amine, and two replace and trisubstituted organic amines.
9. a kind of method that reclaims anhydrous organic amine from organic amine salt according to claim 1 and 2, it is characterized in that: adopt in the described solid-liquid reaction high boiling organic solvent be not with the inertia alkane or the aromatic hydrocarbons of reaction raw materials and product generation chemical reaction, as toluene or heptane etc.
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| CN2010106190139A CN102079712A (en) | 2010-12-31 | 2010-12-31 | Method for recycling anhydrous organic amine from organic amine salt |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183618A (en) * | 2012-11-30 | 2013-07-03 | 大连联化化学有限公司 | Method for recovering dimethylamine from dimethylamine hydrochloride |
| CN109053464A (en) * | 2018-07-23 | 2018-12-21 | 安徽华星化工有限公司 | A method of dimethylamine is recycled from dimethylamine hydrochloride |
| CN112094195A (en) * | 2020-04-15 | 2020-12-18 | 王闻伟 | Separation method of volatile organic alkali |
| CN113200867A (en) * | 2021-05-08 | 2021-08-03 | 中石油吉林化工工程有限公司 | Method for recovering organic amine from organic amine salt aqueous solution |
| CN116062829A (en) * | 2022-12-12 | 2023-05-05 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Non-temperature-changing extraction crystallization desalination method |
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| CN1298855A (en) * | 1999-12-03 | 2001-06-13 | 山东淄博新华－肯孚制药有限公司 | Process for recovering nitrogen-contained organic alkali |
| CN1883790A (en) * | 2006-06-30 | 2006-12-27 | 张家港浩波化学品有限公司 | Process for reclaiming catalyst for use in synthesis of acesulfame potassium |
| CN101007819A (en) * | 2007-01-23 | 2007-08-01 | 句容市兴春化工有限公司 | Silane containing sulfur and its preparing process and application |
| CN101157666A (en) * | 2007-09-12 | 2008-04-09 | 安徽金禾实业股份有限公司 | Triethylamine recovery processing method and device for production of acesulfame potassium |
| WO2008083997A1 (en) * | 2007-01-08 | 2008-07-17 | Basf Se | Method for the production of diphenylmethane diamine |
| CN101293840A (en) * | 2008-04-11 | 2008-10-29 | 兖州市天成化工有限公司 | Process for recovering triethylamine from aqueous solution of triethylamine hydrochloride |
| CN101307002A (en) * | 2008-06-24 | 2008-11-19 | 山东潍坊润丰化工有限公司 | Recovery method of triethylamine in glyphosate mother liquid |
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2010
- 2010-12-31 CN CN2010106190139A patent/CN102079712A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298855A (en) * | 1999-12-03 | 2001-06-13 | 山东淄博新华－肯孚制药有限公司 | Process for recovering nitrogen-contained organic alkali |
| CN1883790A (en) * | 2006-06-30 | 2006-12-27 | 张家港浩波化学品有限公司 | Process for reclaiming catalyst for use in synthesis of acesulfame potassium |
| WO2008083997A1 (en) * | 2007-01-08 | 2008-07-17 | Basf Se | Method for the production of diphenylmethane diamine |
| CN101007819A (en) * | 2007-01-23 | 2007-08-01 | 句容市兴春化工有限公司 | Silane containing sulfur and its preparing process and application |
| CN101157666A (en) * | 2007-09-12 | 2008-04-09 | 安徽金禾实业股份有限公司 | Triethylamine recovery processing method and device for production of acesulfame potassium |
| CN101293840A (en) * | 2008-04-11 | 2008-10-29 | 兖州市天成化工有限公司 | Process for recovering triethylamine from aqueous solution of triethylamine hydrochloride |
| CN101307002A (en) * | 2008-06-24 | 2008-11-19 | 山东潍坊润丰化工有限公司 | Recovery method of triethylamine in glyphosate mother liquid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183618A (en) * | 2012-11-30 | 2013-07-03 | 大连联化化学有限公司 | Method for recovering dimethylamine from dimethylamine hydrochloride |
| CN109053464A (en) * | 2018-07-23 | 2018-12-21 | 安徽华星化工有限公司 | A method of dimethylamine is recycled from dimethylamine hydrochloride |
| CN112094195A (en) * | 2020-04-15 | 2020-12-18 | 王闻伟 | Separation method of volatile organic alkali |
| CN112094195B (en) * | 2020-04-15 | 2023-04-07 | 王闻伟 | Separation method of volatile organic alkali |
| CN113200867A (en) * | 2021-05-08 | 2021-08-03 | 中石油吉林化工工程有限公司 | Method for recovering organic amine from organic amine salt aqueous solution |
| CN116062829A (en) * | 2022-12-12 | 2023-05-05 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Non-temperature-changing extraction crystallization desalination method |
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Application publication date: 20110601 |