CN108358749A - A kind of production method of propargyl alcohol - Google Patents
A kind of production method of propargyl alcohol Download PDFInfo
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- CN108358749A CN108358749A CN201810122581.4A CN201810122581A CN108358749A CN 108358749 A CN108358749 A CN 108358749A CN 201810122581 A CN201810122581 A CN 201810122581A CN 108358749 A CN108358749 A CN 108358749A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention belongs to chemical industry synthesis field more particularly to a kind of production methods of propargyl alcohol, and this method comprises the following steps：(1) formalin and Cu-series catalyst particle are added in reactor, are passed through acetylene gas under stirring condition, are reacted under certain temperature, pressure；Reaction solution respectively obtains Isosorbide-5-Nitrae butynediols and propargyl alcohol through gas-liquid separation；(2) the Isosorbide-5-Nitrae butynediols isolated in step (1) is added in a kettle, solvent, catalyst are added by weight, shuts kettle cover, uses N2After displacement 3 times, heating stirring, synthesis under normal pressure 12 hours stops heating stirring；(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the propargyl alcohol by the reaction solution after separation is rectified purified.Preparation method of the present invention is simple for process, safe, and the propargyl alcohol purity of preparation is more than 99%, and once through yield is up to 23~46%.
Description
Technical field
The invention belongs to chemical industry synthesis field more particularly to a kind of production methods of propargyl alcohol.
Background technology
Propargyl alcohol, also known as 2- propine -1- alcohol, ethynyl carbinol, propilolic alcohol, are a kind of flammable liquids, soluble easily in water, alcohol,
The organic solvents such as ether.Propargyl alcohol is widely used, can be used as the intermediate of organic synthesis, such as synthesizes fosfomycin sodium, fosfomycin calcium, sulphur
Amic metadiazine, methacrylaldehyde, vitamin A etc.；The brightener that can be used as electroplating industry is one of forth generation nickel plating brightener, has
Brightness is higher, and leveling ability is fine, goes out the advantages that ray velocity is fast；It can be used as rust remover or preservative, inhibiting acetic acid, phosphorus
The acidic materials such as acid, sulfuric acid, hydrochloric acid are to having unique performance in terms of the corrosions of metal such as iron, copper, nickel；Also act as solvent,
Stabilizer etc..
Currently, the production technology of propargyl alcohol synthesis is using acetylene, formaldehyde as raw material, copper system is catalyst addition, so
Afterwards by being separated by solid-liquid separation, propargyl alcohol aqueous solution is obtained.Recovered formaldehyde, methanol again, after dehydration, rectifying obtains propilolic alcohol.It synthesizes herein
In technique, Isosorbide-5-Nitrae-butynediols of general by-product 50% or so leads to propargyl alcohol yield about 37%.In order to further enhance alkynes third
Tetrahydrofuran or dimethylformamide may be used as solvent in the yield of alcohol, increase acetylene reaction system concentration, to
The generation of butynediols is reduced, but under high pressure, it brings great potential safety hazard.
Some Domestic BDO enterprises attempt through the existing BDO devices by-product propilolic alcohol of technological transformation, this is a kind of preferable choosing
It selects, but there are a series of problems, such as economy of separation.Therefore, the process of new propargyl alcohol is developed with important
Realistic meaning.
Invention content
Technical problem to be solved by the invention is to provide a kind of producers of propargyl alcohol simple for process, safe
Method is more than 99%, once through yield 23~46% by propargyl alcohol purity prepared by this method.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of production method of propargyl alcohol, includes the following steps：
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
0.5-1.5h is stirred with the rotating speed of 300-500r/min, acetylene gas is passed through, is reacted at 90-120 DEG C, 1.0-2.0MPa；Instead
Reaction solution respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol through gas-liquid separation after answering completely；
(2) Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, solvent, catalysis are added by weight
Kettle cover is shut in agent, uses N2After displacement 3 times, heating stirring, synthesis under normal pressure 1-2 hours stops heating stirring；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
Alcohol.
Preferably, solvent described in step (2) is one or more mixtures in water, liquefied ammonia, organic amine.
Preferably, the organic amine is any one in methylamine, aniline, dimethylamine.
Preferably, the solvent is the mixture of liquefied ammonia and water, and wherein the volume ratio of liquefied ammonia and water is 1:2-6.
Preferably, catalyst described in step (2) is appointing in hydrogen cyanide sodium, potassium hydroxide, cesium hydroxide, calcium hydroxide
Meaning is a kind of, wherein it is preferred that cesium hydroxide.
Preferably, reaction temperature described in step (2) is 80-130 DEG C.
Preferably, mixing speed described in step (2) is 300-800r/min.
Preferably, rectifying described in step (3) includes the following steps：Reaction solution after separation is passed sequentially through into modified bumps
Stick soil and cation exchange column are detached using separating methanol and propilolic alcohol are shared up to the propargyl alcohol, wherein modified concave-convex
Stick soil is prepared by the following method gained：It is added to after attapulgite is crushed in the mixed solution of hydrochloric acid and phosphoric acid, ultrasound is anti-
1-3h, filtering, water washing, drying is answered to obtain attapulgite modified.By it is attapulgite modified can will be present in reaction solution
Trace formaldehyde is converted into methanol, eliminates the separation problem of formaldehyde in subsequent handling, greatly improves product purity.
Compared with prior art, the beneficial effects of the invention are as follows：Present invention process is using Isosorbide-5-Nitrae-butynediols as raw material, liquid
Ammonia, water, organic amine are solvent, and highly basic is catalyst, and 80-130 DEG C of reaction temperature is residence time 1-2 hour, first after the completion of reaction
By being evaporated under reduced pressure separating catalyst, then rectified purified again to obtain propargyl alcohol, catalyst returns to reaction kettle and recycles.This work
Skill has propilolic alcohol high income, and simple for process, safety is good, and obtained propilolic alcohol product purity is more than 99%, and once through yield reaches
To 23~46%.
Specific implementation mode
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
1.5h is stirred with the rotating speed of 300r/min, acetylene gas is passed through, is reacted at 90 DEG C, 1.0MPa；Reaction solution warp after the reaction was complete
Gas-liquid separation respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol；
(2) 100 grams of the Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, 350 milliliters of deionizations are added
Water, 2.0 grams of potassium hydroxide, shuts kettle cover, uses N2After displacement 3 times, heating stirring, at 100 DEG C, constant pressure is reacted 1 hour, is stopped
Heating stirring；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
25 grams of alcohol, once through yield 38.4%.
Embodiment 2
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
1.5h is stirred with the rotating speed of 300r/min, acetylene gas is passed through, is reacted at 90 DEG C, 1.0MPa；Reaction solution warp after the reaction was complete
Gas-liquid separation respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol；
(2) 100 grams of the Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, 100 milliliters of deionizations are added
Water, 200 milliliters of liquefied ammonia, 1.0 grams of cesium hydroxides shut kettle cover, and heating stirring, at 90 DEG C, constant pressure is reacted 2 hours, stops adding
Thermal agitation；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
30 grams of alcohol, once through yield 46.06%.
Embodiment 3
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
1.5h is stirred with the rotating speed of 300r/min, acetylene gas is passed through, is reacted at 90 DEG C, 1.0MPa；Reaction solution warp after the reaction was complete
Gas-liquid separation respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol；
(2) 100 grams of the Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, 100 milliliters of deionizations are added
Water, 200 milliliters of liquefied ammonia, 1.0 grams of cesium hydroxides shut kettle cover, and heating stirring, at 90 DEG C, constant pressure is reacted 2 hours, stops adding
Thermal agitation；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
28 grams of alcohol, once through yield 42.99%.
Embodiment 4
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
1.5h is stirred with the rotating speed of 300r/min, acetylene gas is passed through, is reacted at 90 DEG C, 1.0MPa；Reaction solution warp after the reaction was complete
Gas-liquid separation respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol；
(2) 100 grams of the Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, 50 milliliters of deionizations are added
Water, 300 milliliters of dimethylamine, 2.0 grams of potassium hydroxide shut kettle cover, and heating stirring, at 110 DEG C, constant pressure is reacted 1.5 hours, is stopped
Only heating stirring；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
15 grams of alcohol, once through yield 23.03%.
Embodiment 5
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
1.5h is stirred with the rotating speed of 300r/min, acetylene gas is passed through, is reacted at 90 DEG C, 1.0MPa；Reaction solution warp after the reaction was complete
Gas-liquid separation respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol；
(2) 100 grams of the Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, 100 milliliters of deionizations are added
Water, 200 milliliters of liquefied ammonia, 1.0 grams of cesium hydroxides shut kettle cover, and heating stirring, at 120 DEG C, constant pressure is reacted 2 hours, stops adding
Thermal agitation；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
27 grams of alcohol, once through yield 41.45%.
Embodiment 6
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly,
1.5h is stirred with the rotating speed of 300r/min, acetylene gas is passed through, is reacted at 90 DEG C, 1.0MPa；Reaction solution warp after the reaction was complete
Gas-liquid separation respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol；
(2) 100 grams of the Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, 50 milliliters of deionizations are added
Water, 200 milliliters of methylamines, 1.5 grams of cesium hydroxides shut kettle cover, and heating stirring, at 80 DEG C, constant pressure is reacted 1 hour, stops adding
Thermal agitation；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the alkynes third by the reaction solution after separation is rectified purified
24 grams of alcohol, once through yield 36.85%.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Profit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent requirements of the claims
Variation is included within the present invention.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of production method of propargyl alcohol, which is characterized in that include the following steps：
(1) formalin and Cu-series catalyst particle are added in reactor, use N2Air in metathesis reactor repeatedly, with
The rotating speed of 300-500r/min stirs 0.5-1.5h, is passed through acetylene gas, is reacted at 90-120 DEG C, 1.0-2.0MPa；Reaction
Reaction solution respectively obtains Isosorbide-5-Nitrae-butynediols and propargyl alcohol through gas-liquid separation after completely；
(2) Isosorbide-5-Nitrae-butynediols isolated in step (1) is added in a kettle, solvent, catalyst are added by weight, closes
Upper kettle cover, uses N2After displacement 3 times, heating stirring, synthesis under normal pressure 1-2 hours stops heating stirring；
(3) reaction solution is through vacuum fractionation separating catalyst, then obtains the propargyl alcohol by the reaction solution after separation is rectified purified.
2. the production method of propargyl alcohol according to claim 1, which is characterized in that solvent described in step (2) is water, liquid
One or more mixtures in ammonia, organic amine.
3. the production method of propargyl alcohol according to claim 2, which is characterized in that the organic amine is methylamine, aniline, two
Any one in methylamine.
4. the production method of propargyl alcohol according to claim 2, which is characterized in that the solvent is the mixing of liquefied ammonia and water
Object.
5. the production method of propargyl alcohol according to claim 4, which is characterized in that the volume ratio of the liquefied ammonia and water is 1:
2-6。
6. the production method of propargyl alcohol according to claim 5, which is characterized in that catalyst described in step (2) is cyanogen
Change any one in hydrogen sodium, potassium hydroxide, cesium hydroxide, calcium hydroxide.
7. the production method of propargyl alcohol according to claim 1, which is characterized in that the catalyst is cesium hydroxide.
8. the production method of propargyl alcohol according to claim 1, which is characterized in that reaction temperature is described in step (2)
80-130℃。
9. the production method of propargyl alcohol according to claim 1, which is characterized in that mixing speed is described in step (2)
300-800r/min。
10. the production method of propargyl alcohol according to claim 1, which is characterized in that rectifying described in step (3) includes such as
Lower step：Reaction solution after separation is passed sequentially through into attapulgite modified and cation exchange column, using separating methanol and third
Alkynol is shared to be detached up to the propargyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369328A (en) * | 2018-12-10 | 2019-02-22 | 北京笃敬科技有限公司 | A kind of preparation method of simple and safe synthesis propilolic alcohol |
| CN109456145A (en) * | 2018-12-10 | 2019-03-12 | 北京笃敬科技有限公司 | A kind of system and device and its preparation process of continuous safe and efficient production propilolic alcohol |
| CN112592257A (en) * | 2020-12-21 | 2021-04-02 | 大连理工大学 | Preparation method of coal-based 1, 3-propylene glycol |
| CN115806471A (en) * | 2022-12-15 | 2023-03-17 | 延安大学 | Preparation method for preparing substituted propargyl alcohol by catalyzing paraformaldehyde and alkyne with alkali |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224411A (en) * | 1996-09-03 | 1999-07-28 | 巴斯福股份公司 | Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools |
| CN1558888A (en) * | 2001-09-28 | 2004-12-29 | DSM IP�ʲ�����˾ | Ethynylation process |
| CN1675152A (en) * | 2002-08-16 | 2005-09-28 | 帝斯曼知识产权资产管理有限公司 | Ethynylation process |
| CN1826306A (en) * | 2003-07-24 | 2006-08-30 | 巴斯福股份公司 | Method for the production of propargyl alcohol |
| CN1984860A (en) * | 2004-02-26 | 2007-06-20 | 巴斯福股份公司 | Method for producing a propargyl alcohol and an allyl alcohol |
| CN101277918A (en) * | 2005-09-29 | 2008-10-01 | 帝斯曼知识产权资产管理有限公司 | Cleavage of alkynediols |
-
2018
- 2018-02-07 CN CN201810122581.4A patent/CN108358749B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224411A (en) * | 1996-09-03 | 1999-07-28 | 巴斯福股份公司 | Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools |
| CN1558888A (en) * | 2001-09-28 | 2004-12-29 | DSM IP�ʲ�����˾ | Ethynylation process |
| CN1675152A (en) * | 2002-08-16 | 2005-09-28 | 帝斯曼知识产权资产管理有限公司 | Ethynylation process |
| CN1826306A (en) * | 2003-07-24 | 2006-08-30 | 巴斯福股份公司 | Method for the production of propargyl alcohol |
| CN1984860A (en) * | 2004-02-26 | 2007-06-20 | 巴斯福股份公司 | Method for producing a propargyl alcohol and an allyl alcohol |
| CN101277918A (en) * | 2005-09-29 | 2008-10-01 | 帝斯曼知识产权资产管理有限公司 | Cleavage of alkynediols |
Non-Patent Citations (1)
| Title |
|---|
| 张悦: ""丙炔醇和，4-丁炔二醇的合成工艺研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369328A (en) * | 2018-12-10 | 2019-02-22 | 北京笃敬科技有限公司 | A kind of preparation method of simple and safe synthesis propilolic alcohol |
| CN109456145A (en) * | 2018-12-10 | 2019-03-12 | 北京笃敬科技有限公司 | A kind of system and device and its preparation process of continuous safe and efficient production propilolic alcohol |
| CN112592257A (en) * | 2020-12-21 | 2021-04-02 | 大连理工大学 | Preparation method of coal-based 1, 3-propylene glycol |
| CN115806471A (en) * | 2022-12-15 | 2023-03-17 | 延安大学 | Preparation method for preparing substituted propargyl alcohol by catalyzing paraformaldehyde and alkyne with alkali |
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