CN102924368B - Method of synthesis of 2-picoline through 5-ketohexanenitrile - Google Patents
Method of synthesis of 2-picoline through 5-ketohexanenitrile Download PDFInfo
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- CN102924368B CN102924368B CN201210456105.9A CN201210456105A CN102924368B CN 102924368 B CN102924368 B CN 102924368B CN 201210456105 A CN201210456105 A CN 201210456105A CN 102924368 B CN102924368 B CN 102924368B
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Abstract
The invention provides a method of synthesis of 2-picoline through 5-ketohexanenitrile. According to the method, 5-ketohexanenitrile (acetyl butyronitrile) is utilized as raw materials, with the existence of hydrogen, a particle catalyst is filled in a fixed bed, at the temperature of 380-420 DEG C, under the pressure of 0.02-0.1Mpa, the 2-picoline is synthesized in one step, and each active component of the particle catalyst is Zn1.0CraCubMncKdOe in terms of atomicity. According to the method, with the existence of hydrogen, the 5-ketohexanenitrile raw materials are subjected to hydrogenation, ring closure and dehydrogenation to generate the 2-picoline meanwhile. The method is reasonable in design, high in operability and safe to operate. Due to the method, waster water, waste and waste solid are not generated, and requirement of environment-friendly chemical industry at present is met. According to the method, composite zinc-chromium-manganese-potassium is used as a catalyst, conversion ratio of the 5-ketohexanenitrile can reach 99.0%, molar yield of the 2-picoline can reach 99.0%, and the method can be directly used for synthesizing 2-cyanopridine.
Description
Technical field
The present invention relates to a kind of preparation method of 2-picoline, particularly the method for the synthetic 2-picoline of the own nitrile of a kind of 5-ketone group.
Background technology
2-picoline can be for industries such as agricultural chemicals, medicine, cord fabrics.2-picoline comes from pyridine cut in coal tar in early days, and output is too little, and purity is very low, can not satisfy the demands far away.Pyridine synthesis industrial by-product 2-picoline, output is the 6-8% of pyridine amount, because the maximum purposes of pyridine is synthetic pesticide Paraquat, and Paraquat is limited and progressively superseded, cause the significantly atrophy of pyridine output.Pentanoic also 2-picoline of by-product minute quantity in producing, output is pentanoic 0.6%.Current more advanced technique is that acetonitrile, acetylene are under cyclopentadienyl-cobalt (I)-cyclopentadiene, cyclopentadienyl-cobalt (I)-cyclooctadiene catalysis, pressure 0.8～1.6MPa, 180 ℃ of temperature, there is 2+2+2 ring-closure reaction, generate 2-picoline, the a small amount of benzene of by-product, as described in CN1869023A.This technique disadvantage is acetylene destabilization, with this understanding easily implode.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provide a kind of technological design rationally, the method for excellent catalytic effect, the synthetic 2-picoline of the own nitrile of 5-ketone group that operational safety yield is high.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is the method for the synthetic 2-picoline of the own nitrile of a kind of 5-ketone group, be characterized in: it is raw material that the method be take the own nitrile of 5-ketone group (ethanoyl butyronitrile), under hydrogen exists, loaded particles catalyzer in fixed bed, 380～420 ℃ of temperature, under pressure 0.02～0.1MPa condition, one-step synthesis 2-picoline; The own nitrile load of 5-ketone group is that 40～180g/ rises catalyzer L h, and tail gas acceptance of the bid state hydrogen recycle amount is 0.08～0.2 m
3/ rise catalyzer Lh;
Each active ingredient of beaded catalyst is counted with atomicity:
Zn
1.0Cr
aCu
bMn
cK
dO
e
A value scope is 0.1～1.2;
B value scope is 0.1～0.6;
C value scope is 0.05～0.5;
D value scope is 0.01～0.08;
E is the summation that meets each element oxide requisite oxygen.
In the method and technology scheme of the synthetic 2-picoline of the own nitrile of 5-ketone group of the present invention:
1. in beaded catalyst, zinc preferably comes from zinc subcarbonate, zinc hydroxide; Chromium preferably comes from the sugared reduzate of chromium hydroxide, chromic trioxide; Copper preferably comes from ventilation breather, copper hydroxide; Manganese preferably comes from basic carbonate manganese, manganous hydroxide; Potassium preferably comes from saltpetre, vitriolate of tartar, potassium hydroxide or potassium oxide.
2. in beaded catalyst, a value scope is preferably 0.8～1.0; B value scope is preferably 0.2～0.4; C value scope is preferably 0.1～0.3; D value scope is preferably 0.04～0.06.
3. the beaded catalyst described in preferably adopts method for calcinating preparation, and calcining temperature is preferably 500～650 ℃, more preferably 550～600 ℃.
The own nitrile of 5-ketone group of the present invention (ethanoyl butyronitrile) derives from known method: acetone, the reaction of vinyl cyanide catalyzing and condensing.
Compared with prior art, the inventive method has the following advantages:
1. the inventive method is with the own nitrile of raw material 5-ketone group in the presence of hydrogen, hydrogenation occurs simultaneously, closes ring, dehydrogenation generates 2-picoline again, and it is reasonable in design, workable, operational safety, does not have waste water, discarded, useless solid generation in method, meet the requirement of Modern Green chemical industry.
2. the inventive method is used composite zinc-chromium-copper-manganese-potassium (Zn
1.0cr
acu
bmn
ck
do
e) make catalyzer, make the own nitrile transformation efficiency 99.9% of 5-ketone group, 2-picoline molar yield 99.0%, can be directly used in synthetic 2-cyanopyridine.
Embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, the method for the synthetic 2-picoline of the own nitrile of a kind of 5-ketone group, and it is raw material that the method be take the own nitrile of 5-ketone group (ethanoyl butyronitrile), under hydrogen exists, loaded particles catalyzer in fixed bed, 380 ℃ of temperature, under pressure 0.02MPa condition, one-step synthesis 2-picoline; The own nitrile of 5-ketone group is loaded as 40g/ rises catalyzer L h, and tail gas acceptance of the bid state hydrogen recycle amount is 0.08m
3/ rise catalyzer Lh;
Each active ingredient of beaded catalyst is counted with atomicity:
Zn
1.0Cr
aCu
bMn
cK
dO
e
A value scope is 0.1～1.2;
B value scope is 0.1～0.6;
C value scope is 0.05～0.5;
D value scope is 0.01～0.08;
E is the summation that meets each element oxide requisite oxygen.
Embodiment 2, the method for the synthetic 2-picoline of the own nitrile of a kind of 5-ketone group, and it is raw material that the method be take the own nitrile of 5-ketone group (ethanoyl butyronitrile), under hydrogen exists, loaded particles catalyzer in fixed bed, 420 ℃ of temperature, under pressure 0.1MPa condition, one-step synthesis 2-picoline; The own nitrile of 5-ketone group is loaded as 180g/ rises catalyzer L h, and tail gas acceptance of the bid state hydrogen recycle amount is 0.2 m
3/ rise catalyzer Lh;
Each active ingredient of beaded catalyst is counted with atomicity:
Zn
1.0Cr
aCu
bMn
cK
dO
e
A value scope is 0.1～1.2;
B value scope is 0.1～0.6;
C value scope is 0.05～0.5;
D value scope is 0.01～0.08;
E is the summation that meets each element oxide requisite oxygen.
Embodiment 3, the method for the synthetic 2-picoline of the own nitrile of a kind of 5-ketone group, and it is raw material that the method be take the own nitrile of 5-ketone group (ethanoyl butyronitrile), under hydrogen exists, loaded particles catalyzer in fixed bed, 400 ℃ of temperature, under pressure 0.06MPa condition, one-step synthesis 2-picoline; The own nitrile of 5-ketone group is loaded as 100g/ rises catalyzer L h, and tail gas acceptance of the bid state hydrogen recycle amount is 0.12 m
3/ rise catalyzer Lh;
Each active ingredient of beaded catalyst is counted with atomicity:
Zn
1.0Cr
aCu
bMn
cK
dO
e
A value scope is 0.1～1.2;
B value scope is 0.1～0.6;
C value scope is 0.05～0.5;
D value scope is 0.01～0.08;
E is the summation that meets each element oxide requisite oxygen.
Embodiment 4, in the method for the synthetic 2-picoline of the own nitrile of 5-ketone group described in embodiment 1 or 2 or 3: in beaded catalyst, zinc comes from zinc subcarbonate, zinc hydroxide; Chromium comes from the sugared reduzate of chromium hydroxide, chromic trioxide; Copper comes from ventilation breather, copper hydroxide; Manganese comes from basic carbonate manganese, manganous hydroxide; Potassium comes from saltpetre, vitriolate of tartar, potassium hydroxide or potassium oxide.
Embodiment 5, in the method for the synthetic 2-picoline of the own nitrile of 5-ketone group of embodiment 1-4 described in any one: in beaded catalyst, a value scope is 0.8～1.0; B value scope is 0.2～0.4; C value scope is 0.1～0.3; D value scope is 0.04～0.06.
Embodiment 6, in the method for the synthetic 2-picoline of the own nitrile of 5-ketone group of embodiment 1-5 described in any one: described beaded catalyst adopts method for calcinating preparation, and calcining temperature is 500～650 ℃.
Embodiment 7, in the method for the synthetic 2-picoline of the own nitrile of 5-ketone group of embodiment 1-5 described in any one: described beaded catalyst adopts method for calcinating preparation, and calcining temperature is 550～600 ℃.
Embodiment 8, and the methods experiment 1 of the synthetic 2-picoline of the own nitrile of 5-ketone group adopts fixed-bed process to implement, fixed bed specification (being not limited to this specification): tubulation φ 38 * 3.0 * 3500, amounts to 114, loading catalyst 310 ㎏, fused salt heat exchanging, temperature-controlled precision ± 1 ℃.
Process description is as follows: control 410 ± 1 ℃ of fixed bed catalyst temperature, and 230 ± 10 ℃ of pre-mixing unstripped gas temperature, fixed-bed pressure 0.05MPa, opens cooling heat exchanger and spray absorber trapping product.Nitrogen flow 320m
3/ h(marks state), hydrogen flowing quantity 32m
3/ h(marks state), reduction activation catalyzer, the postactivated end of 10h, closes nitrogen.Continous-stable feeds intake: the own nitrile 31 ㎏/h(79.5mol of 5-ketone group), and circulating hydrogen flow 32m
3/ h(marks state).Trapping product, by liquid chromatography external standard method content and purity.The results are shown in following table:
| Transformation efficiency | 99.9% |
| Molar yield | 99.0% |
| Crude product purity (external standard method) | 99.0% |
Beaded catalyst is preparation technology be described below: following table raw material is dropped into kneader, repeatedly mediate evenly: mixture is in the roasting of aerobic situation, 300～400 ℃ of temperature, time 8～10h; Adding pure water extruded moulding, can be the arbitrary shapes such as spherical, column, open column shape, plum blossom-shaped; Dry; In rotary kiln, 570 ℃ of calcining 6～9h; Obtain beaded catalyst.
| zinc | from zinc subcarbonate, zinc hydroxide. |
| chromium | reduzate from chromium hydroxide, chromic trioxide sugar. |
| copper | from ventilation breather, copper hydroxide. |
| manganese | from basic carbonate manganese, manganous hydroxide. |
| potassium | from saltpetre, vitriolate of tartar, potassium hydroxide, potassium oxide. |
Embodiment 9, the methods experiment 2 of the synthetic 2-picoline of the own nitrile of 5-ketone group, experimental technique is with reference to embodiment 8, experiment parameter with the results are shown in following table.
Embodiment 10, the methods experiment 3 of the synthetic 2-picoline of the own nitrile of 5-ketone group, experimental technique is with reference to embodiment 8, experiment parameter with the results are shown in following table.
Embodiment 11, the methods experiment 4 of the synthetic 2-picoline of the own nitrile of 5-ketone group, experimental technique is with reference to embodiment 8, experiment parameter with the results are shown in following table.
Embodiment 12, the methods experiment 5 of the synthetic 2-picoline of the own nitrile of 5-ketone group, experimental technique is with reference to embodiment 8, experiment parameter with the results are shown in following table.
Embodiment 13, the methods experiment 6 of the synthetic 2-picoline of the own nitrile of 5-ketone group, experimental technique is with reference to embodiment 8, experiment parameter with the results are shown in following table.
Embodiment 14, the methods experiment 7 of the synthetic 2-picoline of the own nitrile of 5-ketone group, experimental technique is with reference to embodiment 8, experiment parameter with the results are shown in following table.
Claims (3)
1. a method for the synthetic 2-picoline of the own nitrile of 5-ketone group, is characterized in that: it is raw material that the method be take the own nitrile of 5-ketone group, under hydrogen exists, loaded particles catalyzer in fixed bed, 380～420 ℃ of temperature, under pressure 0.02～0.1MPa condition, one-step synthesis 2-picoline; The own nitrile load of 5-ketone group is that 40～180g/ rises catalyzer Lh, and tail gas acceptance of the bid state hydrogen recycle amount is 0.08～0.2m
3/ rise catalyzer Lh;
Each active ingredient of beaded catalyst is counted with atomicity:
Zn
1.0Cr
aCu
bMn
cK
dO
e
A value scope is 0.8～1.0; B value scope is 0.2～0.4; C value scope is 0.1～0.3; D value scope is 0.04～0.06; E is the summation that meets each element oxide requisite oxygen; Described beaded catalyst adopts method for calcinating preparation, and calcining temperature is 500～650 ℃.
2. the method for the synthetic 2-picoline of the own nitrile of 5-ketone group according to claim 1, is characterized in that: in beaded catalyst, zinc comes from zinc subcarbonate, zinc hydroxide; Chromium comes from the sugared reduzate of chromium hydroxide, chromic trioxide; Copper comes from ventilation breather, copper hydroxide; Manganese comes from basic carbonate manganese, manganous hydroxide; Potassium comes from saltpetre, vitriolate of tartar, potassium hydroxide or potassium oxide.
3. the method for the synthetic 2-picoline of the own nitrile of 5-ketone group according to claim 1, is characterized in that: calcining temperature is 550～600 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294968A (en) * | 1979-06-29 | 1981-10-13 | The Dow Chemical Company | Method for preparing α-picoline from 5-oxohexanenitrile |
| EP0052898A1 (en) * | 1980-11-15 | 1982-06-02 | Stamicarbon B.V. | Process for the preparation of C-substituted pyridines and/or hydrogenated C-substituted pyridines |
| CN1424144A (en) * | 2002-12-31 | 2003-06-18 | 武汉大学 | Catalyst for preparing 3-cyanopyridine and preparation and use thereof |
| CN101185895A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004105861A (en) * | 2002-09-18 | 2004-04-08 | Koei Chem Co Ltd | Metallic catalyst and production method of pyridine using the same |
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2012
- 2012-11-14 CN CN201210456105.9A patent/CN102924368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4294968A (en) * | 1979-06-29 | 1981-10-13 | The Dow Chemical Company | Method for preparing α-picoline from 5-oxohexanenitrile |
| EP0052898A1 (en) * | 1980-11-15 | 1982-06-02 | Stamicarbon B.V. | Process for the preparation of C-substituted pyridines and/or hydrogenated C-substituted pyridines |
| CN1424144A (en) * | 2002-12-31 | 2003-06-18 | 武汉大学 | Catalyst for preparing 3-cyanopyridine and preparation and use thereof |
| CN101185895A (en) * | 2006-11-17 | 2008-05-28 | 南化集团研究院 | Catalyst for synthesizing low carbon mellow with synthesis gas and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2004-105861A 2004.04.08 |
| 王春翔等.过渡金属催化[2+2+2]环加成反应合成吡啶衍生物.《化学进展》.2010,第22卷(第4期),第610-630页. |
| 过渡金属催化[2+2+2]环加成反应合成吡啶衍生物;王春翔等;《化学进展》;20100424;第22卷(第4期);第610-630页 * |
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