CN1903842A - Preparation method of 3-methyl pyridine - Google Patents
Preparation method of 3-methyl pyridine Download PDFInfo
- Publication number
- CN1903842A CN1903842A CN 200510060202 CN200510060202A CN1903842A CN 1903842 A CN1903842 A CN 1903842A CN 200510060202 CN200510060202 CN 200510060202 CN 200510060202 A CN200510060202 A CN 200510060202A CN 1903842 A CN1903842 A CN 1903842A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- picoline
- methyl piperidine
- gas
- 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.)
- Pending
Links
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 28
- JEGMWWXJUXDNJN-UHFFFAOYSA-N 3-methylpiperidine Chemical compound CC1CCCNC1 JEGMWWXJUXDNJN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229960001866 silicon dioxide Drugs 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- -1 salt salt Chemical class 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
The present invention provides a preparation method of 3-methyl pyridine. Said method is characterized by that it uses 3-methyl piperidine as raw material, uses gas diluting agent as carrier, in the presence of dehydrogenation catalyst makes them implement gas dehydrogenation reaction, its reaction temperature is above 125deg.C, then collects reaction product from reaction mixed gas.
Description
That technical field the present invention relates to is a kind of preparation method of 3-picoline.
Background technology 3-picoline is preparation agricultural chemical insecticide and vitamins B
3---the main raw material of nicotinic acid, niacinamide.At present, the 3-picoline does not still have the method for direct preparation, and mainly be from being to obtain as a kind of by product the process of feedstock production pyridine with formaldehyde, acetaldehyde and ammonia, so limited amount that is provided, and its purification complex procedures has greatly limited the production and the development of 3-picoline subsequent product.
Summary of the invention the present invention is exactly at above-mentioned defective, and a kind of preparation method of 3-picoline is provided, to separate the technical problem that must not be used for suitability for industrialized production.
The preparation method of 3-picoline provided by the invention is to be raw material with the 3-methyl piperidine earlier, is carrier with the diluent for gases, in the presence of dehydrogenation catalyst, do the gas-phase dehydrogenation reaction, temperature of reaction is more than 125 ℃, collecting reaction product from reaction mixture gas then, and its chemical equation:
The preparation method of 3-picoline provided by the invention, the temperature of reaction of said 3-methyl piperidine gas-phase dehydrogenation reaction is 230～350 ℃, preferred 250～300 ℃.Temperature of reaction is lower than 200 ℃, and catalyzer is difficult for inactivation, but feed stock conversion is low; Temperature of reaction is higher than 350 ℃, and the easy coking of catalyzer causes life cycle to shorten, and regeneration is frequent.
The preparation method of 3-picoline provided by the invention, said 3-methyl piperidine gas-phase dehydrogenation reaction is carried out in fixed-bed reactor.As use internal diameter to be 21mm, and long is 3.6m stainless steel tubulation formula reactor, and dehydrogenation catalyst loads wherein, and reactor is outside with the heating of melting salt salt bath.Generally speaking at reactor built-in thermoelectric idol temperature-measuring casing to measure bed temperature.
The preparation method of 3-picoline provided by the invention, said diluent for gases is N
2, water vapor, H
2In a kind of, or two or three mixed gas wherein, preferred H
2
The preparation method of 3-picoline provided by the invention is at 3-methyl piperidine and H
2Mixed gas in 3-methyl piperidine: H
2=1: 1～20 (mole), preferred 1: 2～10 (moles).H in described ratio
2Usage quantity is lower than 1, and side reaction increases, and tar increases, and causes yield to reduce the catalyst carbon deposition inactivation; H
2Usage quantity is higher than 20, and facility investment and working cost increase.
The preparation method of 3-picoline provided by the invention, in the reaction of 3-methyl piperidine gas-phase dehydrogenation, catalyst loading 0.3～1.5g/g catalyzer hr, preferred 0.5～1.0g/g catalyzer hr.
The preparation method of 3-picoline provided by the invention, said dehydrogenation catalyst, be that catalyst component loads on and constitutes on the solid carrier with the precious metal element, catalyst component can adopt well-known methods such as pickling process, ion exchange method to load on the solid carrier.
The preparation method of 3-picoline provided by the invention, the precious metal element of said catalyst component as dehydrogenation catalyst is at least a in platinum, rhodium, iridium, the palladium, preferred palladium.Its charge capacity on carrier is counted 0.1～10% of vehicle weight with element, and preferred 0.3～5%.
The preparation method of 3-picoline provided by the invention, the solid carrier of said dehydrogenation catalyst is silicon-dioxide, porous alumina and alumino silica gel etc.Their Heat stability is goods, the characteristic that aperture and specific surface area are big meets the carrier requirement.Preferred silicon-dioxide.
The preparation method of 3-picoline provided by the invention is 40～800_ as the silicon-dioxide mean pore size of the solid carrier of dehydrogenation catalyst, preferred 100～500_; Specific surface area is 50～500m
2/ g, preferred 100～300m
2/ g.Employed silica supports can be commercially available silicon-dioxide and directly uses, or with known method (as the ammonia treatment method) silicon-dioxide is carried out reaming and handle.
The preparation method of 3-picoline provided by the invention is 0.1～3mm as the carrier particles of silica degree of the solid carrier of dehydrogenation catalyst, preferred 0.3～1.5mm.Granularity is excessive, and to the requirement of strength increase of carrier, and long-time reaction running causes undesired efflorescence easily; Granularity is too small, the reactive behavior height, but increase falls in catalyzer resistance simultaneously, causes reaction conditions wayward.
The preparation method of 3-picoline provided by the invention, adopting the 3-methyl piperidine is raw material, carry out dehydrogenation reaction under gas phase state, and collecting reaction product is simple from reaction mixture gas, as reaction mixture gas is carried out direct condensation; Equally, purified product is also simple, as crude product is distilled, therefore, the invention provides and a kind ofly can directly prepare 3-picoline method, and this method operation is simple, running cost is low is convenient to mass production and is applied to industrialization.
Embodiment 1, elder generation are that raw material mixes with water vapor with the 3-methyl piperidine, make dehydrogenation reaction then in the presence of dehydrogenation catalyst, reclaim reaction product again from reaction mixture gas, and purifying at last promptly gets the 3-picoline.
2, present embodiment provides a kind of preparation process of dehydrogenation catalyst: be averaged aperture 200_ earlier, specific surface area is 250m
2/ g, the silicon-dioxide 350g of granularity 0.75～1.2mm at room temperature is placed on the 1190ml weight concentration and is that dipping took out after 2 hours in 25% the ammoniacal liquor.Joining 3430ml concentration then is in the tetramine palladium nitrate solution of 0.01mol/l, under agitation floods 24hr, takes out the back 110～120 ℃ of oven dry down.Be placed on again in the tube furnace, behind roasting 2hr under 650 ℃ of airflows, at last under 410 ℃ of temperature in H
2Activate 3hr in the atmosphere.So, make that to contain palladium be 1.0% catalyzer.
3, the internal diameter of will packing into by the catalyzer 280g that above method makes is 21mm, longly is 3.6mm, and built-in temperature-measuring casing is in the single tube reactor of external application melting salt salt bath heating.With H
2As carrier gas, mixed gas flow is 260l/hr, and wherein the flow of 3-methyl piperidine is 0.8g/g catalyzer hr, and temperature of reaction is at 293 ℃.Product will be got after the reaction mixture gas condensation, stability for the check product, analysis to this product is carried out after preserving 120 hours, analysis is carried out with gas-chromatography, analytical results is: 3-methyl piperidine transformation efficiency 91.6%, and yield 90.1% promptly contains 3-picoline 90.1% in the product, 3-methyl piperidine 8.4%, other organism 1.5%.Product by fractionation by distillation, is returned unreacted 3-methyl piperidine through with distillation purification 3-picoline as raw material.
Following table has been enumerated by embodiment 2,3 identical steps and prepared catalyzer and the embodiment of the Different Results that obtains under different reaction process condition:
| Embodiment | Palladium charge capacity (%) in the dehydrogenation catalyst | Two cyaniding silicon specific surface area (m 2/g) | 3-methyl piperidine flow (g/g catalyzer hr) | Temperature of reaction (℃) | 3-methyl piperidine transformation efficiency (%) | 3-picoline yield (%) |
| 4 | 0.5 | 300 | 0.8 | 330 | 94.2 | 91.3 |
| 5 | 0.5 | 500 | 0.6 | 255 | 88.2 | 87.4 |
| 6 | 1.0 | 300 | 0.8 | 350 | 96.5 | 90.8 |
| 7 | 5.0 | 120～160 | 1.0 | 275 | 90.8 | 89.6 |
| 8 | 5.0 | 250～275 | 1.4 | 300 | 93.4 | 91.8 |
Claims (12)
1, a kind of preparation method of 3-picoline is characterized in that being raw material with the 3-methyl piperidine earlier, is carrier with the diluent for gases, in the presence of dehydrogenation catalyst, do the gas-phase dehydrogenation reaction, temperature of reaction is more than 125 ℃, collecting reaction product from reaction mixture gas then, and its chemical equation:
2, the preparation method of 3-picoline as claimed in claim 1 is characterized in that the temperature of reaction of said 3-methyl piperidine gas-phase dehydrogenation reaction is 230～350 ℃.
3, the preparation method of 3-picoline as claimed in claim 1 or 2 is characterized in that the temperature of reaction of said 3-methyl piperidine gas-phase dehydrogenation reaction is 250～300 ℃.
4, the preparation method of 3-picoline as claimed in claim 1 is characterized in that said diluent for gases, is N
2, water vapor, H
2At least a among the three.
5,, it is characterized in that said diluent for gases is H as the preparation method of claim 1 or 4 described 3-picolines
2
6, the preparation method of 3-picoline as claimed in claim 1 is characterized in that at 3-methyl piperidine and H
2Mixed gas in 3-methyl piperidine: H
2=1: 1～20 (mole).
7, as the preparation method of claim 1 or 6 described 3-picolines, it is characterized in that at 3-methyl piperidine and H
2Mixed gas in 3-methyl piperidine: H
2=1: 2～10 (moles).
8,, it is characterized in that catalyst loading is 0.3～1.5g/g catalyzer hr in the reaction of 3-methyl piperidine gas-phase dehydrogenation as the preparation method of claim 1 or 6 described 3-picolines.
9, the preparation method of 3-picoline as claimed in claim 7 is characterized in that catalyst loading is 0.5～1.0g/g catalyzer hr in the reaction of 3-methyl piperidine gas-phase dehydrogenation.
10, the preparation method of 3-picoline as claimed in claim 1, what it is characterized in that said catalyst component as dehydrogenation catalyst is palladium, as the solid carrier of dehydrogenation catalyst is silicon-dioxide.
11, the preparation method of 3-picoline as claimed in claim 8 is characterized in that the charge capacity of said palladium on the catalysis dehydrogenation agent carrier count 0.1～10% of vehicle weight with element; The mean pore size of said silicon-dioxide is 40～800_, and specific surface area is 50～500m
2/ g, granularity is 0.1～3mm.
12, the preparation method of 3-picoline as claimed in claim 8 or 9 is characterized in that the charge capacity of said palladium on the catalysis dehydrogenation agent carrier count 0.3～5% of vehicle weight with element; The mean pore size of said silicon-dioxide is 100～500_, and specific surface area is 100～300m
2/ g, granularity is 0.3～1.5mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510060202 CN1903842A (en) | 2005-07-29 | 2005-07-29 | Preparation method of 3-methyl pyridine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510060202 CN1903842A (en) | 2005-07-29 | 2005-07-29 | Preparation method of 3-methyl pyridine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1903842A true CN1903842A (en) | 2007-01-31 |
Family
ID=37673224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510060202 Pending CN1903842A (en) | 2005-07-29 | 2005-07-29 | Preparation method of 3-methyl pyridine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1903842A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011045014A2 (en) | 2009-10-16 | 2011-04-21 | Lonza Ltd | Catalysts for the preparation of methylpyridine |
| CN102164895A (en) * | 2008-09-26 | 2011-08-24 | 帝斯曼知识产权资产管理有限公司 | Method for the preparation of 3-methylpyridine |
| CN102295595A (en) * | 2011-05-10 | 2011-12-28 | 浙江爱迪亚营养科技开发有限公司 | Method for producing pyridine compound |
| CN102471268A (en) * | 2009-07-29 | 2012-05-23 | 隆萨有限公司 | Process for the selective preparation of 3-methylpyridine from acrolein and one or more ammonium salts dissolved in water |
| CN102803215A (en) * | 2009-06-24 | 2012-11-28 | 隆萨有限公司 | Synthesis process for 3-methylpyridine |
| US8530664B2 (en) | 2009-10-16 | 2013-09-10 | Lonza Ltd. | Catalysts for the preparation of methylpyridine |
| CN107935832A (en) * | 2017-12-30 | 2018-04-20 | 郑州智谷工业技术有限公司 | A kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal |
| CN112844377A (en) * | 2021-02-01 | 2021-05-28 | 铂尊投资集团有限公司 | Production method of 3-methylpyridine, composite catalyst and preparation method |
| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
| CN114105869A (en) * | 2022-01-24 | 2022-03-01 | 苏州开元民生科技股份有限公司 | Preparation method of 2-propyl-4-cyanopyridine |
-
2005
- 2005-07-29 CN CN 200510060202 patent/CN1903842A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164895A (en) * | 2008-09-26 | 2011-08-24 | 帝斯曼知识产权资产管理有限公司 | Method for the preparation of 3-methylpyridine |
| CN102803215A (en) * | 2009-06-24 | 2012-11-28 | 隆萨有限公司 | Synthesis process for 3-methylpyridine |
| CN102803215B (en) * | 2009-06-24 | 2014-04-30 | 隆萨有限公司 | Synthesis process for 3-methylpyridine |
| CN102471268A (en) * | 2009-07-29 | 2012-05-23 | 隆萨有限公司 | Process for the selective preparation of 3-methylpyridine from acrolein and one or more ammonium salts dissolved in water |
| WO2011045014A2 (en) | 2009-10-16 | 2011-04-21 | Lonza Ltd | Catalysts for the preparation of methylpyridine |
| US8530664B2 (en) | 2009-10-16 | 2013-09-10 | Lonza Ltd. | Catalysts for the preparation of methylpyridine |
| EP2322273A1 (en) | 2009-10-16 | 2011-05-18 | Lonza Ltd. | Catalysts for the preparation of methylpyridine |
| CN102295595A (en) * | 2011-05-10 | 2011-12-28 | 浙江爱迪亚营养科技开发有限公司 | Method for producing pyridine compound |
| CN102295595B (en) * | 2011-05-10 | 2013-06-05 | 浙江爱迪亚营养科技开发有限公司 | Method for producing pyridine compound |
| CN107935832A (en) * | 2017-12-30 | 2018-04-20 | 郑州智谷工业技术有限公司 | A kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal |
| CN112844377A (en) * | 2021-02-01 | 2021-05-28 | 铂尊投资集团有限公司 | Production method of 3-methylpyridine, composite catalyst and preparation method |
| CN112844377B (en) * | 2021-02-01 | 2021-10-01 | 铂尊投资集团有限公司 | Production method of 3-methylpyridine, composite catalyst and preparation method |
| CN113617354A (en) * | 2021-07-08 | 2021-11-09 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof |
| WO2023280276A1 (en) * | 2021-07-08 | 2023-01-12 | 南京红太阳生物化学有限责任公司 | 3-methylpiperidine dehydrogenation catalyst, and preparation method therefor and application thereof |
| GB2624128A (en) * | 2021-07-08 | 2024-05-08 | Nanjing Redsun Biochemistry Co Ltd | 3-Methylpiperidine dehydrogenation catalyst, and preparation method therefor and application thereof |
| CN114105869A (en) * | 2022-01-24 | 2022-03-01 | 苏州开元民生科技股份有限公司 | Preparation method of 2-propyl-4-cyanopyridine |
| CN114105869B (en) * | 2022-01-24 | 2022-11-08 | 苏州开元民生科技股份有限公司 | Preparation method of 2-propyl-4-cyanopyridine |
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