CN1289488C - Method of preparing 2-cyanopyrazine by ammonia oxidation method and its special catalyst - Google Patents
Method of preparing 2-cyanopyrazine by ammonia oxidation method and its special catalyst Download PDFInfo
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- CN1289488C CN1289488C CN 03101166 CN03101166A CN1289488C CN 1289488 C CN1289488 C CN 1289488C CN 03101166 CN03101166 CN 03101166 CN 03101166 A CN03101166 A CN 03101166A CN 1289488 C CN1289488 C CN 1289488C
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- China
- Prior art keywords
- ammonia
- catalyzer
- catalyst
- methylpyrazine
- ammonia oxidation
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Abstract
The present invention discloses an ammonia oxidation method and a special catalyst for preparing 2-carbonitrile. The active component of the special catalyst is VaTibPcDdEeOx, vanadium and titanium are used as main catalysts, phosphorus, ferrum, nickel, cobalt, bismuth, manganese, chromium, molybdenum, cuprum, zincum, tin, boron, kalii, lithium, magnesium, etc. are used as auxiliary catalysts. The catalyst is used for preparing 2-carbonitrile by the ammonia oxidation method, and the special catalyst has the advantages of high activity, good selectivity, high output rate of products, high purity, simple technology, etc.
Description
One, technical field
The present invention relates to method and special-purpose catalyst that a kind of oxidation proceses of ammonia prepares 2 cyano pyrazine, it belongs to technical field of organic chemistry, also belongs to organic fine chemical technical field.
Two, background technology
2 cyano pyrazine, molecular formula C
5H
3N
3, white or light yellow liquid under the normal temperature.Be applied to industries such as medicine, spices.
Because the 2-methylpyrazine makes 2 cyano pyrazine through oxidative ammonolysis under catalyst action is the method for preparing the best of cyano group compounds at present, its key is to find the catalyzer of high reactivity, highly selective.Ammonia oxidation is meant under catalyst action, labile methyl group in the organic molecule and cheap ammonia and oxygen (air) reaction, and a step is converted into the catalyzed reaction of cyano group.The preparation of employing oxidation proceses of ammonia, 2 cyano pyrazine have technology simple and direct, can carry out continuously, advantage such as throughput is strong, environmentally friendly and raw material is easy to get, other traditional synthesis that alternative route is long, energy consumption is high, environmental pollution is serious is produced the method for 2 cyano pyrazine.At present, using oxidation proceses of ammonia in the world prepares the 2 cyano pyrazine method and does not appear in the newspapers, domestic rarely seen TQ463 report adopts the CP-2 loaded catalyst to carry out the research that the direct ammonia oxidation of 2-methylpyrazine prepares 2 cyano pyrazine, and suitable temperature of reaction is 430 ℃, and reactant ratio is n (NH
3): n (O
2): n (H
2O)=1: (10～15): 2: 5, it was about 90% to reach reaction conversion ratio, and the 2 cyano pyrazine selectivity is about 80%.
Three, summary of the invention
The purpose of this invention is to provide method and special-purpose catalyst that a kind of ammonia oxidation prepares 2 cyano pyrazine, this catalyzer answers that cost is low, thermostability and physical strength are good, better selectivity of tool and activity can improve the transformation efficiency of 2-methylpyrazine and the productive rate of 2 cyano pyrazine.
For realizing that the present invention adopts following measure:
A kind of ammonia oxidation prepares the catalyzer of 2 cyano pyrazine, and it is to be Primary Catalysts with vanadium, titanium, and phosphorus, iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, copper, zinc, tin, boron, potassium, lithium, magnesium etc. are the multicomponent catalyst of helping agent, and it consists of: V
aTi
bP
cD
dE
eO
x/ SiO
2, wherein P is that phosphorus, D are iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, E is copper, zinc, tin, boron, potassium, lithium or magnesium; A=1; B=0.3～2.5; C=0.5～1.7; D=0～1.2; E=0～0.9; X then decides according to the content of above each element.Active ingredient element wt content is 5～30%, and preferably scope is 8～20%.Carrier is a microsphere silica gel, and the microsphere diameter scope is 125～450m.
Preparation of catalysts adopts pickling process: oxide compound, salt or the alkali of each element of the effective constituent of catalyzer dissolved respectively, mixes, fully flood the back stirring with carrier silica gel again, and still aging, under suitable temperature, activate certain hour then.Generally between 713～903K, preferably temperature range is 763～843K to activation temperature.Soak time was generally 4～12 hours, and the optimum activating time scope is 5～11 hours.
Preparation is during catalyzer, and each component can be with oxide compound, salt or the alkali etc. of this element.For example vanadium can be used NH
4VO
3, titanium can be used TiCl
4, Ti
2(C
2O
4)
3Deng, phosphorus can be used H
3PO
4, (NH
4)
3PO
4, (NH
4)
2HPO
4, (NH
4) H
2PO
4Or P
2O
5Deng, manganese can be used MnO
2, MnCl
2, Mn (NO
3)
2Deng, chromium can be used CrCl
3, Cr (NO
3)
39H
2O, Cr
2O
3, CrO
3Or (NH
4)
2Cr
2O
7Deng, molybdenum can be used MoO
3, (NH
4)
6Mo
7O
24Deng, iron can be used FeCl
3, Fe
2O
3, Fe
3O
4, Fe (NO
3)
39H
2O, Fe (OAc)
2, Fe (C
2O
4) 2H
2O or Fe
2(C
2O
4) 6H
2O etc., copper can be used CuCl
2Or Cu (NO
3)
2Deng, zinc can be used ZnO, ZnCl
2, Zn (NO
3)
2Or Zn (OAc)
22H
2O etc., tin can be used SnCl
2Or SnCl
4Deng, boron can be used H
3BO
3, potassium can be used KOH, KCl, KNO
3, K
2CO
3Or K
2C
2O
4Deng, lithium can be used Li
2O, LiCl, LiNO
3Or Li
2CO
3Deng, magnesium can be used MgO, MgCl
2Or Mg (NO
3)
26H
2O etc.
The optimum process condition scope of the open catalyzer oxidative ammonolysis of the present invention is as follows: temperature of reaction 633～713K, the mol ratio of air and 2-methylpyrazine is 8～60, the mol ratio of ammonia and 2-methylpyrazine is 2～12, catalyst loading 30～100g (kgcath).Be that the transformation efficiency of 2-methylpyrazine can be higher than 97.0% on the steel pipe fixed-bed reactor of 30mm and under the stable reaction conditions at internal diameter, the molar yield of 2 cyano pyrazine can be up to 88.5%, and product purity is higher than 97.0%.
Adopting with vanadium, titanium among the present invention is Primary Catalysts, phosphorus, iron, nickel, cobalt, bismuth, chromium, molybdenum, copper, zinc, tin, boron, potassium, lithium, magnesium etc. are five component catalysts of promotor, can make the 2-methylpyrazine make 2 cyano pyrazine, the method that traditional synthesis that can alternative route is long, energy consumption is high, environmental pollution is serious is produced 2 cyano pyrazine through oxidative ammonolysis one step.Simultaneously, this catalyzer uses silica gel to make carrier, face carrier silica gel can provide the effective ratio area and the pore structure of catalyzed reaction, the thermostability and the physical strength of catalyzer have been improved greatly, reduced the usage quantity of catalyst activity component, the Preparation of catalysts cost is reduced, on fixed bed and fluidized-bed reactor, all can use.
Four, embodiment
Below in conjunction with embodiment, the technology of the present invention is described in further detail.
Embodiment 1
With 4.431 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, adds the TiCl of 1.11 grams, 85% strong phosphoric acid, 3.211 gram vanadium and 11.60mL 0.139mol/L then respectively
4Solution after the uniform solution to be formed, is poured solution into 30 gram silica gel (among the Φ 125～425um).Stir, after the drying, in muffle furnace, progressively be warmed up to 550 ℃, calcination 10 hours with 70 ℃ heat-up rate per hour.Standby behind the naturally cooling.Consisting of of catalyzer: V
1Ti
1.3P
0.5/ SiO
2, activity of such catalysts composition weight content is 10%.
At internal diameter is the above-mentioned solid catalyst of filling 15g in the steel pipe fixed-bed reactor of 30mm, and the mole proportioning of reaction raw materials is the 2-methylpyrazine: ammonia: air=1: 6: 15, temperature of reaction are 683K, and the load of catalyzer is 50g/ (kgcath).After reacting for 15 seconds, the transformation efficiency 89.7% of 2-methylpyrazine, the molar yield of 2 cyano pyrazine is 81.2%, and the selectivity of 2 cyano pyrazine is 81.8%, and product purity is 97.5%.
Embodiment 2～4: catalyzer is formed different, and processing condition are with embodiment 1, result such as following table:
| Embodiment | Catalyzer | Transformation efficiency % | Productive rate % | Selectivity % |
| 2 | V 1Ti 0.4P 1.4Bi 0.1/SiO 2 | 97.7 | 83.4 | 83.5 |
| 3 | V 1Ti 1.8P 0.4K 0.2/SiO 2 | 98.4 | 84.2 | 84.7 |
| 4 | V 1Ti 21P 0.8Cr 0.2/SiO 2 | 98.2 | 85.7 | 86.4 |
Embodiment 5
With 4.403 gram H
2C
2O
42H
2O is dissolved under 85 ℃ in the 30mL distilled water, sweeps then not add 4.4296 grams, 85% strong phosphoric acid, 3.132 gram vanadium, behind the dark blue solution to be formed, adds TiCl O.139mol/L
4Solution 2.65mL, 50%Mn (NO
3)
2Solution 2.2946mL and O.1202 restrain LiCl after the uniform solution to be formed, pours solution rapidly in the 30 gram silicon (Φ 125～425 μ m).Stir, placement is spent the night.In High Temperature Furnaces Heating Apparatus, progressively be warmed up to 550 ℃, calcination 1O hour.After treating naturally cooling, preserve stand-by.Consisting of of this catalyzer: V
1Ti
0.3P
1.6Mn
0.25Li
0.2/ SiO
2, activity of such catalysts composition weight content is 10%.
The 15g catalyzer is packed in the internal diameter 30mm steel pipe fixed-bed reactor, and material mixed gas passes through catalyst bed reaction.Consisting of of material mixed gas: 2-methylpyrazine: ammonia: air=1: 6: 20.Temperature of reaction is 683K, and the load of catalyzer is 50g/ (kgcath).After reacting for 15 seconds, 2-methylpyrazine transformation efficiency 97.1%, 2 cyano pyrazine productive rate 87.5%, selectivity 90.3%, product purity 97.7%.Major impurity in the product is pyrazinoic acid amide and the pyrazine-2-formic acid that the 2-methylpyrazine generates in ammonia oxidation.
Embodiment 6～7: catalyzer is formed different, and processing condition are with embodiment 5, result such as following table:
| Embodiment | Catalyzer | Transformation efficiency % | Productive rate % | Selectivity % |
| 6 | V 1Ti 2.2P 0.7Fe 0.2Mg 0.1/SiO 2 | 98.3 | 86.9 | 87.5 |
| 7 | V 1Ti 0.9P 0.5Cu 0.1B 0.15/SiO 2 | 97.7 | 87.7 | 88.9 |
Claims (4)
1, a kind of oxidation proceses of ammonia prepares the catalyzer of 2 cyano pyrazine, and it is to be carrier with silica gel, it is characterized in that: this catalyst activity composition consists of: V
aTi
bP
cD
dE
eO
x, wherein P=phosphorus, D=iron, nickel, cobalt, bismuth, manganese, chromium, molybdenum, E=copper, zinc, tin, boron, potassium, lithium or magnesium; A=1; B=0.3～2.5; C=0.5～1.7; D=0～1.2; E=0～0.9; X then decides according to the content and the valence state of above each element.
2, catalyzer according to claim 1 is characterized in that: the content of its active ingredient element is: 5～30%.
3, catalyzer according to claim 1 and 2 is characterized in that: the content of its active ingredient element is 8～20%.
4, oxidation proceses of ammonia prepares the method for 2 cyano pyrazine, it is characterized in that: oxide compound, salt or the alkali of each element of the active principle of claim 1 are dissolved mixing respectively, with carrier silica gel dipping, fully stirring, still aging again, between 713～903K, activate 4～12 hours then; The processing condition of ammonia oxidation: temperature of reaction 633～713K, the mol ratio of air and 2-methylpyrazine is 8～60, ammonia and 2-methylpyrazine mol ratio are 2～12, catalyst loading 30～100g/ (kgcath).
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|---|---|---|---|
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| CN1289488C true CN1289488C (en) | 2006-12-13 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427473C (en) * | 2006-11-21 | 2008-10-22 | 浙江大学 | Synthesis method of key intermediate 2-cyanpyrazine of tuberculosis drug pyrazinamide |
| US20130245310A1 (en) * | 2012-03-13 | 2013-09-19 | Celanese International Corporation | Catalyst for producing acrylic acids and acrylates |
| CN106111172B (en) * | 2016-06-22 | 2018-06-15 | 徐州恒鼎生物科技有限公司 | Catalyst for preparing 3-cyanopyridine by catalytic ammoxidation and preparation method thereof |
| CN109482211A (en) * | 2017-09-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of catalyst and preparation method thereof for synthesizing 2 cyano pyrazine |
| CN111410636A (en) * | 2020-03-30 | 2020-07-14 | 苏州弘森药业股份有限公司 | Preparation process of pyrazinamide |
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