CN113548995A - Preparation method of alpha-pyrrolidone - Google Patents
Preparation method of alpha-pyrrolidone Download PDFInfo
- Publication number
- CN113548995A CN113548995A CN202110993690.5A CN202110993690A CN113548995A CN 113548995 A CN113548995 A CN 113548995A CN 202110993690 A CN202110993690 A CN 202110993690A CN 113548995 A CN113548995 A CN 113548995A
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- CN
- China
- Prior art keywords
- reaction
- preparation
- reaction product
- pyrrolidone
- butyrolactone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000012432 intermediate storage Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- RWYGQIQKHRMKFH-UHFFFAOYSA-N naphthalene;sulfuric acid Chemical compound OS(O)(=O)=O.C1=CC=CC2=CC=CC=C21 RWYGQIQKHRMKFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 238000004176 ammonification Methods 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NGUGWHFIVAQVMN-UHFFFAOYSA-N 4-aminobut-3-en-2-one Chemical compound CC(=O)C=CN NGUGWHFIVAQVMN-UHFFFAOYSA-N 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- GMZVRMREEHBGGF-UHFFFAOYSA-N Piracetam Chemical compound NC(=O)CN1CCCC1=O GMZVRMREEHBGGF-UHFFFAOYSA-N 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
Abstract
The invention discloses a preparation method of alpha-pyrrolidone, which comprises the following steps of (1) respectively pumping gamma-butyrolactone and ammonia water into a pipeline from a material storage tank by a metering pump, and feeding the gamma-butyrolactone and the ammonia water into a mixer through the pipeline to be mixed to obtain a mixed material; (2) feeding the mixed material into a preheating device for preheating, then feeding the mixed material into a tubular fixed bed reactor for reaction, and simultaneously adding a catalyst into the reactor; (3) heating the tubular fixed bed reactor to fully react the mixed materials, and obtaining a reaction product after the reaction is finished; (4) and cooling the reaction product by a heat exchanger, then sending the reaction product into a constant pressure tank for depressurization treatment, releasing the pressure and then sending the reaction product into an intermediate storage tank to release the surplus ammonia, and returning the collected surplus ammonia to the reaction system again. The preparation method of the alpha-pyrrolidone with the structure has the advantages of small catalyst dosage, low price, reduced cost, high reaction speed, simple production process, mild reaction conditions and high safety.
Description
Technical Field
The invention relates to the technical field of preparation of fine chemical products, in particular to a preparation method of alpha-pyrrolidone.
Background
Alpha-pyrrolidone of formula C4H7NO is an efficient and excellent organic solvent, is an important chemical raw material, and is widely applied to the industries of medicine, textile, dye, coating, cosmetics and the like, such as manufacturing Naofukang, nylon 4, polyvinylpyrrolidone, artificial blood plasma and the like. The existing synthesis methods of alpha-pyrrolidone comprise a 1-butanolamine oxidation dehydration method, a 1, 4-butanedioic acid ammonification reduction method, a 1-chlorobutyryl chloride ammonification method, a 1, 4-butyrolactone ammonification method and the like, but the only production method for realizing industrialization at present is the 1, 4-butyrolactone ammonification method, but the prior art has the following defects of high reaction pressure and temperature, very high requirements on equipment design, low reaction conversion rate and yield and high operation and production cost.
Disclosure of Invention
The invention aims to provide a preparation method of alpha-pyrrolidone, and the catalyst has the advantages of small dosage, low price, reduced cost, high reaction speed, simple production process, mild reaction conditions and high safety.
In order to achieve the above object, the present invention provides a method for preparing α -pyrrolidone, 1. a method for preparing α -pyrrolidone, comprising the steps of:
(1) respectively pumping gamma-butyrolactone and ammonia water into a pipeline from a storage tank by a metering pump, and mixing in a mixer through the pipeline to obtain a mixed material;
(2) feeding the mixed material into a preheating device for preheating, then feeding the mixed material into a tubular fixed bed reactor for reaction, and simultaneously adding a catalyst into the reactor;
(3) heating the tubular fixed bed reactor to fully react the mixed materials, and obtaining a reaction product after the reaction is finished;
(4) and cooling the reaction product by a heat exchanger, then sending the reaction product into a constant pressure tank for depressurization treatment, releasing the pressure, sending the decompressed reaction product into an intermediate storage tank to release surplus ammonia, returning the collected surplus ammonia into the reaction system again, and separating and purifying the crude product in the intermediate storage tank by a three-stage continuous tower to obtain the product.
Preferably, in the step (1), the molar ratio of the gamma-butyrolactone to the ammonia water is 1:1 to 1: 1.2.
Preferably, in the step (2), the catalyst is an inorganic and organic acid composition solution, and the catalyst is any one or two of boric acid, benzoic acid, naphthalene sulfuric acid, proline, phthalic acid and p-toluenesulfonic acid.
Preferably, in the step (2), the addition amount of the catalyst accounts for 0.3-10% of the addition amount of the gamma-butyrolactone.
Preferably, in the step (3), the reaction temperature is 220-260 ℃.
Therefore, the preparation method of the alpha-pyrrolidone with the structure has the advantages of small catalyst dosage, low price, low cost, high reaction speed, simple production process, mild reaction conditions and high safety.
The technical solution of the present invention is further described in detail by the following examples.
Detailed Description
The present invention will be further described with reference to examples, in which various chemicals and reagents are commercially available unless otherwise specified.
Examples
Respectively pumping gamma-butyrolactone and ammonia water into a pipeline from a storage tank by a metering pump, wherein the molar ratio of the addition amount of the gamma-butyrolactone and the ammonia water is 1:1.1, the gamma-butyrolactone and the ammonia water enter a mixer through the pipeline and are mixed to obtain a mixed material, feeding the mixed material into a preheating device for preheating, feeding the preheated mixed material into a tubular fixed bed reactor for reaction, and simultaneously adding a catalyst p-toluenesulfonic acid into the reactor, wherein the addition amount of the catalyst is 3% of the addition amount of the gamma-butyrolactone; heating the tubular fixed bed reactor to 230 ℃ for reaction, fully reacting for 1.5h, and obtaining a reaction product after the reaction is finished; and cooling the reaction product by a heat exchanger, then sending the reaction product into a constant pressure tank for depressurization treatment, releasing the pressure, sending the decompressed reaction product into an intermediate storage tank to release surplus ammonia, returning the collected surplus ammonia into the reaction system again, and separating and purifying the crude product in the intermediate storage tank by a three-stage continuous tower to obtain the product.
The product obtained in this example had a yield of 99.11% and a purity of 99.39%.
Therefore, the preparation method of the alpha-pyrrolidone with the structure has the advantages of small catalyst dosage, low price, low cost, high reaction speed, simple production process, mild reaction conditions and high safety.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (5)
1. A preparation method of alpha-pyrrolidone is characterized by comprising the following steps:
(1) respectively pumping gamma-butyrolactone and ammonia water into a pipeline from a storage tank by a metering pump, and mixing in a mixer through the pipeline to obtain a mixed material;
(2) feeding the mixed material into a preheating device for preheating, then feeding the mixed material into a tubular fixed bed reactor for reaction, and simultaneously adding a catalyst into the reactor;
(3) heating the tubular fixed bed reactor to fully react the mixed materials, and obtaining a reaction product after the reaction is finished;
(4) and cooling the reaction product by a heat exchanger, then sending the reaction product into a constant pressure tank for depressurization treatment, releasing the pressure, sending the decompressed reaction product into an intermediate storage tank to release surplus ammonia, returning the collected surplus ammonia into the reaction system again, and separating and purifying the crude product in the intermediate storage tank by a three-stage continuous tower to obtain the product.
2. A process for the preparation of an α -pyrrolidone according to claim 1, wherein: in the step (1), the molar ratio of the gamma-butyrolactone to the ammonia water is 1: 1-1: 1.2.
3. A process for the preparation of an α -pyrrolidone according to claim 1, wherein: in the step (2), the catalyst is inorganic and organic acid composition solution, and the catalyst is any one or two of boric acid, benzoic acid, naphthalene sulfuric acid, proline, phthalic acid and p-toluenesulfonic acid.
4. A process for the preparation of an α -pyrrolidone according to claim 3, wherein: in the step (2), the adding amount of the catalyst accounts for 0.3-10% of the adding amount of the gamma-butyrolactone.
5. A process for the preparation of an α -pyrrolidone according to claim 1, wherein: in the step (3), the reaction temperature is 220-260 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110993690.5A CN113548995A (en) | 2021-08-27 | 2021-08-27 | Preparation method of alpha-pyrrolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110993690.5A CN113548995A (en) | 2021-08-27 | 2021-08-27 | Preparation method of alpha-pyrrolidone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113548995A true CN113548995A (en) | 2021-10-26 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110993690.5A Pending CN113548995A (en) | 2021-08-27 | 2021-08-27 | Preparation method of alpha-pyrrolidone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113548995A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117185979A (en) * | 2023-09-11 | 2023-12-08 | 北京恒瑞新霖科技有限公司 | A kind of preparation method of energy-saving pyrrolidone |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO108561B1 (en) * | 1992-05-18 | 1994-06-30 | Sc Chimcomplex Sa | 2-pyrolidone continuous process of preparation |
| CN1104635A (en) * | 1993-12-27 | 1995-07-05 | 化学工业部北京化工研究院 | Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone |
| WO1999052866A1 (en) * | 1998-04-09 | 1999-10-21 | Pantochim S.A. | A process for the production of 2-pyrrolidone in a continous fashion, starting from gamma butyrolactone and ammonia |
| CN104496878A (en) * | 2014-12-02 | 2015-04-08 | 铜仁学院 | Method for catalyzing and synthesizing alpha-pyrrolidone by using granular solid superacid |
| CN104725293A (en) * | 2015-02-11 | 2015-06-24 | 沈阳化工大学 | Continuous production method of alpha-pyrrolidone |
-
2021
- 2021-08-27 CN CN202110993690.5A patent/CN113548995A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO108561B1 (en) * | 1992-05-18 | 1994-06-30 | Sc Chimcomplex Sa | 2-pyrolidone continuous process of preparation |
| CN1104635A (en) * | 1993-12-27 | 1995-07-05 | 化学工业部北京化工研究院 | Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone |
| WO1999052866A1 (en) * | 1998-04-09 | 1999-10-21 | Pantochim S.A. | A process for the production of 2-pyrrolidone in a continous fashion, starting from gamma butyrolactone and ammonia |
| CN104496878A (en) * | 2014-12-02 | 2015-04-08 | 铜仁学院 | Method for catalyzing and synthesizing alpha-pyrrolidone by using granular solid superacid |
| CN104725293A (en) * | 2015-02-11 | 2015-06-24 | 沈阳化工大学 | Continuous production method of alpha-pyrrolidone |
Non-Patent Citations (1)
| Title |
|---|
| 翟林峰: "N-乙烯基吡咯烷酮合成新工艺研究", 《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117185979A (en) * | 2023-09-11 | 2023-12-08 | 北京恒瑞新霖科技有限公司 | A kind of preparation method of energy-saving pyrrolidone |
| CN117185979B (en) * | 2023-09-11 | 2024-08-09 | 北京恒瑞新霖科技有限公司 | Preparation method of energy-saving pyrrolidone |
| WO2025055007A1 (en) * | 2023-09-11 | 2025-03-20 | 北京恒瑞新霖科技有限公司 | Method for preparing energy-saving pyrrolidinone |
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Application publication date: 20211026 |