CN102584597B - Cleaner production method for cyclopropylamine - Google Patents
Cleaner production method for cyclopropylamine Download PDFInfo
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- CN102584597B CN102584597B CN201110456805.3A CN201110456805A CN102584597B CN 102584597 B CN102584597 B CN 102584597B CN 201110456805 A CN201110456805 A CN 201110456805A CN 102584597 B CN102584597 B CN 102584597B
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- Prior art keywords
- cyclopropylamine
- caustic soda
- clean preparation
- solution
- production method
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- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 65
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000292 calcium oxide Substances 0.000 claims abstract description 8
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- AIMMVWOEOZMVMS-UHFFFAOYSA-N cyclopropanecarboxamide Chemical compound NC(=O)C1CC1 AIMMVWOEOZMVMS-UHFFFAOYSA-N 0.000 claims description 10
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 9
- 238000010025 steaming Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 5
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000004571 lime Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 230000008719 thickening Effects 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 3
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract 1
- AWQVKAURKXXOCG-UHFFFAOYSA-N n-cyclopropylformamide Chemical compound O=CNC1CC1 AWQVKAURKXXOCG-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940124307 fluoroquinolone Drugs 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a cleaner production method for cyclopropylamine. The production method comprises the following steps of: cooling a cyclopropyl formamide aqueous solution to below 0 DEG C, dripping a sodium hypochlorite aqueous solution while controlling reaction temperature to be 0 to 5 DEG C, preserving heat, adding quick lime and caustic soda liquid, raising temperature, reacting and distilling to obtain cyclopropylamine vinasse, evaporating to low temperature to obtain a mixed solution of cyclopropylamine and water, and rectifying the cyclopropylamine solution to obtain a finished product cyclopropylamine. After the reaction, the whole system is an aqueous solution consisting of cyclopropylamine, sodium carbonate, sodium hydroxide, sodium chloride and a small amount of by-product, and all the components are recycled by distillation, filtering, decoloration, concentration and filtering, so that the aim of making the best use of everything and the aim of cleaner production are fulfilled.
Description
Technical field
The present invention relates to a kind of preparing fluoroquinolone compound class antibacterials.More specifically, the present invention relates to a kind of clean preparation method of cyclopropylamine.
Background technology
At present the production technique of cyclopropylamine is similar, employing be all that through Hofmann, degraded makes the operational path of cyclopropylamine by cyclopropyl carboxamide.The basic raw material that this classical technique adopts, except main raw material cyclopropyl carboxamide, also has clorox and liquid caustic soda.Concrete production process is: the cyclopropyl carboxamide aqueous solution is chilled to below 0 ℃, drips aqueous sodium hypochlorite solution, add rear insulation 2 hours, drip and holding temperature 0-5 ℃, after insulation finishes, add liquid caustic soda, heat up and steam cyclopropylamine finished product.The advantage of above-mentioned technique is good reaction selectivity, yield is higher, but shortcoming is that the raffinate amount after distillation is larger, and comparison of ingredients complexity, contain sodium carbonate, sodium hydroxide, sodium-chlor, also have the Multiple components such as byproduct of reaction, this waste water treatment difficulty is larger, treatment cost is higher, has become for many years the bottleneck that cyclopropylamine further expands the scale of production.
And be also badly in need of in the market solving wastewater problem in cyclopropylamine production process.
Summary of the invention
The present invention, on the basis that cyclopropylamine production technique is furtherd investigate, explores a kind of clean preparation method of cyclopropylamine.
Technical scheme of the present invention is as follows:
A kind of clean preparation method of cyclopropylamine, described production method comprises the steps: the cyclopropyl carboxamide aqueous solution to be chilled to below 0 ℃, drip aqueous sodium hypochlorite solution, during dropping, control temperature of reaction 0-5 ℃, add rear insulation, after described insulation finishes, add unslaked lime and liquid caustic soda, temperature reaction and distillation obtain cyclopropylamine vinasse, steaming is to end temperature, and the solution steaming is the mixed solution of cyclopropylamine and water, and cyclopropylamine water liquid is through the rectifying cyclopropylamine that gets product.
Another aspect of the present invention, described cyclopropylamine vinasse is adopted with the following method and is processed: cold filtration obtains calcium carbonate, activated carbon decolorizing, thickening filtration obtains sodium-chlor, and filtrate is for reclaiming liquid caustic soda.
Another aspect of the present invention, described recovery liquid caustic soda can mix and be re-used in production method separately and with fresh liquid caustic soda.
Another aspect of the present invention, described steaming is to end temperature to 110 ℃.
Another aspect of the present invention, according to mass percent meter, the ratio of described unslaked lime and cyclopropyl carboxamide is 1: 1.
Another aspect of the present invention, described unslaked lime is calcium lime powder.
In vinasse, mainly contain and be insoluble in the calcium carbonate of water, sodium-chlor soluble in water and a small amount of catalyzer sodium hydroxide, also have a small amount of organic reaction by product.Vinasse is cooling, filter to obtain calcium carbonate (can make material of construction), filtrate is with concentrating precipitated sodium chloride after activated carbon decolorizing, again filter to obtain solid sodium chloride (can make industrial salt sells), filtrate is aqueous sodium hydroxide solution (recovery liquid caustic soda), can overlap for next batch and react.
Beneficial effect of the present invention is: the clean preparation method of cyclopropylamine of the present invention makes not produce in production process pollution with unslaked lime, and can Circulation, without waste liquid, effectively makes waste water treatment, and has improved the productive rate of producing.The present invention has reacted the aqueous solution that rear whole system is cyclopropylamine, sodium carbonate, sodium hydroxide, sodium-chlor and a small amount of by product composition, can above-mentioned each component be recycled by methods such as distilling, filter, decolour, concentrate, refilter, thereby realized, make the best use of everything, the target of cleaner production.
Embodiment
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited to this:
Embodiment mono-:
By 80g (98.0%, cyclopropyl carboxamide 0.922mol) adds in the there-necked flask of 1000ml, add 400ml water, stirring and dissolving, be chilled to-5 ℃, start to drip the aqueous sodium hypochlorite solution of 605.6g (10.8% available chlorine), drip process control temp at 0-5 ℃, after dripping off, 0-5 ℃ is incubated 2 hours.Add catalyzer liquid caustic soda 20.0g (30%, 0.15mol), add 80g calcium lime powder (85.0%, 1.214mol), stirring heats up is distilled to 110 ℃ of still temperature, finishes distillation.The above-mentioned cyclopropylamine water liquid filled column steaming is carried out to rectifying and obtain certified products cyclopropylamine 41.1g (99.5%), also obtain in addition substandard products cyclopropylamine 11.2g (65.8%), add up to two portions product must roll over hundred cyclopropylamine 48.3g, yield 91.9%.
Vinasse is cooled to room temperature, filter to obtain calcium carbonate, filtrate adds in 1000ml there-necked flask, adds 10.0g gac, stirs 30 minutes, by gac elimination, filtrate rejoins 1000ml there-necked flask, and stirring heats up is concentrated into about 150ml, cooling, filter to obtain sodium-chlor, filtrate is the aqueous sodium hydroxide solution containing a small amount of sodium-chlor.
Embodiment bis-:
The cyclopropyl carboxamide of 80g (98%, 0.922mol) is added in the there-necked flask of 1000ml, add the water of 400ml, stirring and dissolving, be chilled to-5 ℃, start to drip the aqueous sodium hypochlorite solution of 622.9g (10.5% available chlorine), drip process control temp at 0-5 ℃.After dripping off, 0-5 ℃ is incubated 2 hours.Add the sodium hydroxide solution 33.0g (18.2% containing a small amount of sodium-chlor reclaiming in above-mentioned " embodiment mono-", 0.15mol), add 80g calcium lime powder (85.0%, 1.214mol), stirring heats up is distilled to 110 ℃ of still temperature, finishes distillation.The above-mentioned cyclopropylamine water liquid filled column steaming is carried out to rectifying and obtain certified products cyclopropylamine 40.5g (99.6%), obtain in addition substandard products cyclopropylamine 12.0g (64.6%), two portions product adds up to obtain rolls over hundred cyclopropylamines 48.1%.Yield 91.4%.Vinasse is processed with " embodiment mono-".
Embodiment tri-:
By 80g (98.0%, cyclopropyl carboxamide 0.922mol) adds in the there-necked flask of 1000ml, add 400ml water, stirring and dissolving, be chilled to-5 ℃, start to drip the aqueous sodium hypochlorite solution of 654.0g (10.0% available chlorine), drip process control temp at 0-5 ℃, after dripping off, 0-5 ℃ is incubated 2 hours.Add the aqueous sodium hydroxide solution 14.9g (20.2% that contains a small amount of sodium-chlor reclaiming in " embodiment mono-", 0.075mol), add again fresh alkali lye 10.0g (30%, 0.075mol), add 80g calcium lime powder (85.0%, 1.214mol), stirring heats up is distilled to 110 ℃ of still temperature, finishes distillation.The above-mentioned cyclopropylamine water liquid filled column steaming is carried out to rectifying and obtain certified products cyclopropylamine 40.0g (99.5%), obtain in addition substandard products cyclopropylamine 13.2g (60.6%), two portions product adds up to obtain rolls over hundred cyclopropylamine 47.8g, yield 91.0%.Vinasse is processed with " embodiment mono-".
So far invention has been described in conjunction with the embodiments.Those skilled in the art should be appreciated that without departing from the scope and spirit of the present invention, can easily to described embodiment, make various other modifications.Therefore, the scope of appended claims is not limited to above-mentioned explanation, but will broadly explain claim.
Claims (6)
1. the clean preparation method of a cyclopropylamine, described production method comprises the steps: the cyclopropyl carboxamide aqueous solution to be chilled to below 0 ℃, drip aqueous sodium hypochlorite solution, during dropping, control temperature of reaction 0-5 ℃, add rear insulation, it is characterized in that: after described insulation finishes, add unslaked lime and liquid caustic soda, temperature reaction and distillation obtain cyclopropylamine vinasse, steaming is to end temperature, and the solution steaming is the mixed solution of cyclopropylamine and water, and cyclopropylamine water liquid is through the rectifying cyclopropylamine that gets product.
2. the clean preparation method of a kind of cyclopropylamine as claimed in claim 1, is characterized in that: described cyclopropylamine vinasse is adopted with the following method and processed: cold filtration obtains calcium carbonate, activated carbon decolorizing, and thickening filtration obtains sodium-chlor, and filtrate is for reclaiming liquid caustic soda.
3. the clean preparation method of a kind of cyclopropylamine as claimed in claim 1, is characterized in that: described recovery liquid caustic soda can mix and be re-used in production method separately and with fresh liquid caustic soda.
4. the clean preparation method of a kind of cyclopropylamine as claimed in claim 1, is characterized in that: described steaming is to end temperature to 110 ℃.
5. the clean preparation method of a kind of cyclopropylamine as claimed in claim 1, is characterized in that: according to mass percent meter, the ratio of described unslaked lime and cyclopropyl carboxamide is 1: 1.
6. the clean preparation method of a kind of cyclopropylamine as claimed in claim 1, is characterized in that: described unslaked lime is calcium lime powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110456805.3A CN102584597B (en) | 2011-12-27 | 2011-12-27 | Cleaner production method for cyclopropylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110456805.3A CN102584597B (en) | 2011-12-27 | 2011-12-27 | Cleaner production method for cyclopropylamine |
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| CN102584597A CN102584597A (en) | 2012-07-18 |
| CN102584597B true CN102584597B (en) | 2014-04-16 |
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| CN201110456805.3A Active CN102584597B (en) | 2011-12-27 | 2011-12-27 | Cleaner production method for cyclopropylamine |
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| CN109264886A (en) * | 2018-09-17 | 2019-01-25 | 大丰跃龙化学有限公司 | A kind of wastewater treatment method in cyclopropylamine production process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125715A (en) * | 1995-09-28 | 1996-07-03 | 金旭虎 | Industrial production method of cyclopropylamine |
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2011
- 2011-12-27 CN CN201110456805.3A patent/CN102584597B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125715A (en) * | 1995-09-28 | 1996-07-03 | 金旭虎 | Industrial production method of cyclopropylamine |
Non-Patent Citations (3)
| Title |
|---|
| 王树良等.环丙胺的合成.《中国医药工业杂志》.1993,第24卷(第11期),514-516. |
| 环丙胺的合成;王树良等;《中国医药工业杂志》;19931231;第24卷(第11期);514-516 * |
| 赵学清等.环丙胺的合成.《中国医药工业杂志》.1994,第25卷(第5期),225-226. * |
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| CN102584597A (en) | 2012-07-18 |
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Denomination of invention: Clean production method of cyclopropylamine Effective date of registration: 20230427 Granted publication date: 20140416 Pledgee: Taizhou Linhai sub branch of Bank of Communications Co.,Ltd. Pledgor: Zhejiang Shaxing Technology Co.,Ltd. Registration number: Y2023330000807 |
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