CN1044338C - Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use - Google Patents

Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use Download PDF

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CN1044338C
CN1044338C CN94106416A CN94106416A CN1044338C CN 1044338 C CN1044338 C CN 1044338C CN 94106416 A CN94106416 A CN 94106416A CN 94106416 A CN94106416 A CN 94106416A CN 1044338 C CN1044338 C CN 1044338C
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cyanopyridine
oxide
picoline
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CN1106314A (en
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林启欣
吴贵勤
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BEIJING CHEMICAL INST MINISTRY OF CHEMICAL INDUSTRY
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Abstract

The invention discloses a catalyst for preparing cyanopyridine and a preparation method of the cyanopyridine. The catalyst uses V, Ti and Sb oxide as main active material, at least one oxide of P, SnB, Ag, Zr, rare earth element and mixed rare earth element as cocatalyst, optionally at least one oxide of alkali metal as stabilizer, and has high activity, good selectivity and long service life.

Description

Catalyzer of preparing cyanopyridine by ammoxidation of alkyl-pyridine and uses thereof
The present invention relates to a kind of is raw material with the alkyl pyridine, prepares the catalyzer of corresponding cyanopyridine through gas phase ammonoxidation.In particular, what the present invention relates to is raw material with 3-or 4-picoline, prepares the catalyzer of corresponding cyanopyridine in molecular oxygen and water vapour atmosphere through gas phase ammonoxidation.
The 3-cyanopyridine is the intermediate of preparation nicotinic acid, niacinamide, and the 4-cyanopyridine is an intermediate of making Yi Yansuan, Isonicotinamide, vazadrine.Nicotinic acid, niacinamide are a kind of of vitamins B, are extensive use of in industries such as medicine, food and fodder additives.The vazadrine is an anti-tuberculosis drugs.
The preparation method of cyanopyridine is known, referring to U.S.4, and 284,781,4,447,612,4,963,687 and 5,028,713; JP74-34673 (special permission bulletin) and JP82-156038.
Lummus company is at U.S.4, discloses fusion Vanadium Pentoxide in FLAKES carried catalyst in 284, No. 781, and cigarette nitrile selectivity is 89.7%, and per pass conversion is 51%, and this catalyst selectivity is poor, and transformation efficiency is low and need cyclic regeneration.Degussa company is at U.S.4, and the oxide compound of having described with Sb and V in 447, No. 612 is the catalyzer of main active substance, and this catalyst activity substances content is up to 48%, and complicated process of preparation and ammonia consumption are big, and the alkyl pyridine transformation efficiency is low.Japan touches that coal chemical industry company proposed with silicon carbide in JP74-34673 number be carrier, V-Ti is main active substance, with P, Nb, K, Cs, Ti, Zn, Gd is the catalyzer of promotor, and the sintered silicon carbon that this catalyzer employing purity is 98-99% is a carrier, the cost height.The yield of cigarette nitrile and different cigarette nitrile is not high, and has a small amount of unreacted alkyl pyridine in the reactant gases, influences aftertreatment technology.Mitsubishi gas chemical company is at U.S, 4,963, and disclosing a kind of oxide compound with V, Cr and B in No. 687 is main active substance, and the oxide compound of P and/or Mo is the SiO of promotor 2Carried catalyst, this catalyst activity, selectivity is all not high.Standard Oil Company is at U.S.5, and disclosing with P, V and Mo metal oxide in 028, No. 713 is main active substance, and Sb, Fe, W, Cu, K, Cs, B, Sn, Zr, Mn, Nb, U, Bi and Cr are the SiO of promotor 2Carried catalyst.This activity of such catalysts is low, and the alkyl pyridine transformation efficiency is not high.Up to the present, do not have a kind of catalyzer of prior art to have the transformation efficiency height, selectivity is good, the premium properties that the life-span is long.
Therefore, the purpose of this invention is to provide a kind of from the method for alkyl pyridine with high conversion and the corresponding cyanopyridine of highly-selective preparation.
Another object of the present invention provides a kind of catalyzer of novelty, and it is in the use of the inventive method, and selectivity is good, the transformation efficiency height, and the life-span is long.
A further object of the present invention is that the preparation method of preparation new catalyst used in the present invention is provided.
Other purpose of the present invention, the feature and advantage of others can be clearer at reading specification sheets and claim postscript.
The invention provides a kind of method for preparing cyanopyridine, it is to make corresponding alkyl pyridine, reacts in the presence of catalyzer with the gas and the water vapor of ammonia, molecule-containing keto.This catalyzer is with V 2O 5, TiO 2And Sb 2O 3Be main active substance, at least a oxide compound of P, Sn, B, Ag, Zr, rare earth element and lucium is a promotor, selectively adds alkali-metal at least a oxide compound as stablizer, and it is stated from the heat-stable inert support.
New catalyst of the present invention, main active substance are V 2O 5, TiO 2And Sb 2O 3, its grammeatom ratio is: at least a oxide compound of V: Ti: Sb=1: 3-56: 0.1-1.0, P, Sn, B, Ag, Zr and rare earth element and lucium is a promotor, its grammeatom ratio to V is 0.001-0.3: 1.Preferred Ag, Sn, La and Ce, more preferably mixed rare-earth oxide.
In above-mentioned composition, selectively add alkali-metal at least a oxide compound, further improve selectivity of catalyst and thermostability.The preferred Li of basic metal, Na, K, Rb, Cs, more preferably K, Rb, to the grammeatom of V than being 0.001-0.1.The preferred 5-20% (Wt) of catalyst activity substances content 1-30% (Wt), catalyzer of the present invention does not in use need regeneration, and the life-span reaches 3 years.
The raw material for preparing catalyst activity material of the present invention can be used oxide compound, muriate, inorganic salt such as nitrate, carbonate, phosphoric acid salt, vitriol, ammonium salt etc.; Organic salt such as oxalate, acetate and amine salt etc. and oxide compound, oxyhydroxide.Those skilled in the art can determine arbitrarily.
Employed TiO 2Can be commercially available TiO 2, also can be in order to TiCl 4Be the highly active TiO of raw material with the known method preparation 2Perhaps their composition.TiO 2Be anatase titanium dioxide, specific surface is 3-100m 2/ g is preferably 5-50m 2/ g, particle diameter are preferably 0.01-0.3 μ less than 1 μ.
The employed carrier of catalyzer of the present invention is the solid material of heat-stable inertia, as talcum (britesorb), fused alumina, silicon carbide, quartz and pottery etc., preferably talc and silicon carbide.Carrier can be sphere, cylindrical, annular, preferred spherical.The carrier diameter is 3-12mm, preferred 3-8mm.Carrier can be atresia or vesicular structure, and its porosity is 0-80%, preferred 0-50%.
Catalyzer of the present invention can prepare with known method in the present technique field.For example, with the salt and the oxide dissolution of vanadium and various promotors or be suspended in water and organic solvent in, organic solvent such as ethanol, thanomin, methane amide, ethanamide, diethylamide, urea and ammonium sulfocyanate etc. add TiO 2, the suspension of preparation active substance.Carrier is placed the coating pan that rotating and the rotating machinery of other type, suspension is dripped or sprays on the exsiccant carrier, till active substance reaches pre-metering.Catalyzer was 400-500 ℃ of activation 2-10 hour.
Method of the present invention can use 2-picoline, 3-picoline, 4-picoline, 2-methyl-5-ethylpyridine and 2-ethyl-5-picoline to be raw material.
The ammoxidation of alkyl-pyridine reaction is to carry out in the fixed bed single tube reactor, and tube inner diameter is 21-40mm, long 1-4m, and the catalyzer loading amount is the 0.4-1.2 liter, is thermophore with the fused salt that circulates, the bed temperature thermocouple measurement.The processing condition of reaction are:
Air speed 1000-3000hr -1
Alkyl pyridine concentration 20-80g/NM 3
Alkyl pyridine: ammonia=1: 1-10 (mole ratio)
Alkyl pyridine: water vapor=1: 1-20 (mole ratio)
Temperature of reaction: 300 ℃-450 ℃
In material gas mixture, if air is used as oxygen-containing gas, the concentration of alkyl pyridine can be 20-100g/NM 3, preferred 40-70g/NM 3
Employed ammonia amount in material gas mixture surpasses theoretical amount.When using a large amount of ammonia, must reclaim unreacted ammonia, preferred employed ammonia amount is theoretical amount 2-8 times.
The amount of oxygen is at least theoretical 1.5 times in material gas mixture, is preferably 2-30 times of theoretical amount.Usually air is as oxygen-containing gas, and air can be used the inert gas dilution of nitrogen and so on, CO 2Also can be used as diluent gas with water vapor.
Temperature of reaction is 300-450 ℃, and when being lower than 300 ℃, the transformation efficiency of alkyl pyridine is low, when being higher than 450 ℃, generates CO 2Amount big, the yield of cyanopyridine is low.Preferable reaction temperature is 340 ℃-400 ℃.
This reaction is under atmospheric pressure carried out usually, also can carry out being higher than normal atmosphere or being lower than under the normal atmosphere.
From reaction mixture gas, reclaim reaction product and can adopt suitable method, as reaction mixture gas being cooled to reaction product solidified temperature.Or water or The suitable solvent washing reaction product, to reclaim it, these all are known methods.
The present invention utilizes following limiting examples to further specify, and all percentage ratios are weight percentage.Except as otherwise noted.
Example 1
With 18 gram V 2O 5Add in the 400ml deionized water that contains 45 gram oxalic acid, heating for dissolving is made the oxalic acid vanadyl aqueous solution of avy blue.In this solution, add 17.3 gram Sb 2O 3, 1.34 the gram AgNO 3, 1.4 gram Ce 2(C 2O 4) 39H 2O, 80 gram methane amides and specific surface are 10m 2The anatase titanium dioxide TiO of/g 2253 grams stir and make active substance suspension.
With diameter is 6mm, and porosity is 5% talcum ball carrier, 1000 grams, adds diameter and is in the coating pan of rotation of 300mm, with the suspension spraying of active substance or be added drop-wise on the exsiccant carrier, reaches till 10% up to the catalyst activity substances content.Then under air atmosphere in 460 ℃ of activation 6 hours, the grammeatom ratio that the catalyst activity material that makes is formed is:
V∶Ti∶Sb∶Ag∶Ce=1∶16∶0.6∶0.04∶0.02
At internal diameter is filling 1000ml catalyzer in the single tube reactor of the long 3.6m boiler steel of 25mm control, and bed height is 2.2m, is raw material with 3-or 4-picoline, and prepared by ammoxidation 3-or 4-cyano group pyrrole are fixed, processing condition and the results are shown in Table 1.
Raw material and product gc analysis, data are to react sampling result (as follows) after 10 days in the table.
Table 1
Air speed: 1500hr -1
Water: 3-or 4-picoline=10: 1 (mole ratio)
Picoline transformation efficiency :~100%*
*~100% the expression>99.97% following example in if no special instructions the picoline transformation efficiency be~100%.
3-picoline concentration g/NM 3 4-methyl pyrrole is decided concentration g/NM 3 Temperature of reaction ℃ Ammonia: 3-or 4-picoline mole ratio 3-cyanopyridine yield mol% 4-cyanopyridine yield mol%
40 60 / / 380 380 2.5∶1 2.5∶1 90.5 90.3 / /
/ / 50 60 360 355 2∶1 2∶1 / / 91.5 92.3
Example 2
Remove Ce 2(C 2O 4) 39H 2O is outside 0.7 gram, adds La (NO again 3) 36H 2O 0.68 gram, Praseodymium trioxide (Pr 6O 11) 0.067 gram, other is with example 1, and 3-picoline concentration is 60g/NM 3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield is 90.7mol%.
Example 3
Divided by mixed rare-earth oxide (with A xO yExpression, it consists of: 24-26%La 2O 348-52%CeO 25-17%Nd 2O 35-7%Pr 6O 11Sm 2O 3, Gd 2O 3, sum<2%) replaced C e 2(C 2O 4) 39H 2Outside the O, other is with example 1.The rare earth oxide amount is in cerium oxide, so V: A=1: 0.02 (grammeatom ratio), the AxOy add-on is 0.68 gram, 3-picoline concentration is 60g/NM 3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield is 91.1mol%.
Example 4
The catalyst activity material consists of: 18 gram V 2O 5, 45 gram oxalic acid, 11.5 gram Sb 2O 3, 1.34 the gram AgNO 3, 0.51 the gram mixed rare-earth oxide, 0.23 the gram Rb 2CO 3, specific surface is 10m 2The TiO of/g 2285 grams, methane amide 50 grams, ethanol 50 grams, 450 milliliters of deionized waters, this Preparation of catalysts method and reaction unit and processing condition are with example 1, and test-results sees Table 2.
Table 2*
Air speed hr -1 3-picoline concentration g/NM 3 4-methyl pyrrole is decided concentration g/NM 3 Temperature of reaction ℃ 3-cyanopyridine yield mol% 4-cyanopyridine yield mol%
1500 1500 1600 1600 40 60 / / / / 50 60 385 380 365 360 92.1 91.7 / / / / 92.7 94.1
Example 5
Except that Silver Nitrate replaced with primary ammonium phosphate, nitric acid tin, boric acid and zirconium white, other was with example 4, and test-results sees Table 3.
Table 3*
V: promotor grammeatom ratio Air speed hr -1 3-methyl pyrrole is decided concentration g/NM 3 Temperature of reaction ℃ 3-cyanopyridine yield mol%
V∶P=1∶0.08 1500 1500 40 60 385 380 91.9 91.5
V∶Sn=1∶0.06 1500 1500 40 60 385 380 91.0 91.2
V∶B=1∶0.04 1400 40 385 90.2
V∶Zr=1∶0.04 1400 40 385 90.5
Example 6
Except that not adding the rare-earth oxidation beyond the region of objective existence, other are with example 4, and test-results sees Table 4:
Table 4
3-picoline concentration g/NM 3 Temperature of reaction ℃ 3-picoline transformation efficiency % 3-cyanopyridine yield mol%
40 385 ~100 88.5
60 385 98.6 88.9*
*: calculate with the 3-picoline that has transformed.
Example 7
Remove with 0.77 gram CsNO 3Replace Pb 2CO 3Outward, other is with example 4,3-or 4-picoline concentration 50g/nm 3, 385 ℃, 365 ℃ of temperature of reaction, 3-cyanopyridine yield is that 91.2mol%, 4-cyanopyridine yield are 93.6mol%.
Example 8
With the Sb in the 18.7 gram vanadic acid antimony replacement examples 4 2O 3With 7.2 gram V 2O 5, or with 20.1 gram antimony oxalates replacement Sb 2O 3, experimental result sees Table 5.
Table 5
Contain the antimony material Day in reaction times 3-picoline concentration g/NM 3 Temperature of reaction ℃ 3-picoline yield mol%
Antimonous oxide 5 10 50 50 390 385 88.3 91.7
Antimony oxalate 5 10 50 50 385 385 90.6 91.7
Vanadic acid antimony 5 10 50 50 385 385 91.5 91.8
By in the table as can be known, add the inductive phase that vanadic acid antimony or antimony oxalate can reduce catalyzer.
Example 9
285 gram specific surfaces in example 4 are 10M 2The TiO of/g 2, reduce to 158 gram (V: Ti=1: 10) and wherein contain 10% by TiCl 4The active TiO of preparation 2, other are with example 4, and test-results sees Table 6.
Table 6
3-picoline concentration g/NM 3 4-picoline concentration g/NM 3 Temperature of reaction 3-cyanopyridine yield mol% 4-cyanopyridine yield mol%
50 70 / / / / 50 70 375 370 355 350 91.4 91.9 / / / / 91.8 93.1
As can be known from Table 6, add active TiO 2, can suitably reduce temperature of reaction, improve the load of catalyzer.
Example 10
Except that adopting talcum ring, silicon carbide ball, alumina balls, quartz sand ball, Ceramic Balls is the carrier, and other are with example 4.Test-results sees Table 7.
Table 7
The kind of carrier transitivity 3-picoline concentration g/NM 3 Temperature of reaction ℃ 3-cyanopyridine yield mol%
Content % Particle diameter mm Porosity %
Talcum cyclohexyl carbodiimide silicon ball alumina balls quartz sand ball porcelain ball Talcum powder>65 SiC>85 α-Al 2O>85 quartz sands>80 porcelain powder>90 φ6×6×1.5 φ6 φ5 φ5 φ5 5-10 35-40 35-40 20-25 0-10 60 60 60 40 40 385 380 380 380 380 91.8 91.6 91.1 89.1 91.4
Fully aware of, those skilled in the art can carry out various modifications or improvement to the present invention by above-mentioned description and discussion, but do not break away from the spirit and scope of foregoing description, or the scope of claims.
Comparative example 1
18 gram V 2O 5, 19.3Sb 2O 3, specific surface~10m 2The anatase titanium dioxide TiO of/g 2285 grams, 1000 gram φ 6mm talcum balls prepare catalyzer, catalyst activity material grammeatom ratio: V: Ti: Sb=1 with the method for example 1: 18: 0.6, with the testing apparatus of example 1.
At air speed 1500hr -1, 3-picoline concentration 40g/NM 3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield 86.5mol%.
Comparative example 2
18 gram V 2O 5, 1.4 gram Ce 2(C 2O 4) 39H 2O, 285 gram specific surface~10m 2/ g, anatase titanium dioxide TiO 2, 1000 gram φ 6mm silicon carbide balls, prepare catalyzer with example 1 method, catalyst activity material grammeatom ratio: V: Ti: Ce=1: 18: 0.02, test with the experimental installation of example 1, the results are shown in Table 8.
Table 8
Air speed 3-methyl pyrrole concentration g/NM 3 4-picoline concentration g/NM 3 Temperature of reaction ℃ 3-cyanopyridine yield mol% 4-cyanopyridine yield mol%
1500 1500 1600 1600 40 60 / / / / 50 60 375 375 355 355 87.2 88.6 / / / / 90.4 89.7
Comparative example 3
18 gram V 2O 5, 1.34 the gram AgNO 3, 285 gram specific surface~10m 2/ g and anatase titanium dioxide TiO 2, 1000 gram φ 6mm talcum ball carriers, prepare catalyzer and carry out the evaluating catalyst test with example 1 method, at air speed 1500hr -1, 3-picoline concentration 50g/NM 3, 380 ℃ of temperature of reaction, 3-cyanopyridine yield 84.8mol%.

Claims (16)

1. the catalyzer of the corresponding cyanopyridine of ammoxidation of alkyl-pyridine system is with V 2O 5, TiO 2And Sb 2O 3Be main active constituent, its grammeatom is than being V: Ti:Sb=1: 3-56: 0.1-1.0, and promotor is to be selected from least a oxide compound of P, Sn, B, Ag, Zr, rare earth element and lucium or their combination; Its grammeatom ratio to V is 0.001-0.3: 1, be stated from the inorganic carrier, and the content of the activity of such catalysts component that makes is 1-30%, by weight;
Wherein inorganic carrier is to be selected from a kind of in talcum, silicon carbide, fused alumina, quartz sand and the pottery.
2. by the catalyzer of claim 1, wherein activity of such catalysts component content is 5-20%, by weight.
3. by the catalyzer of claim 1, wherein rare earth oxide is CeO 2
4. by the catalyzer of claim 1, rare earth oxide wherein is La 2O 3, CeO 2And Pr 6O 11
5. by the catalyzer of claim 1, the consisting of of mixed rare-earth oxide wherein: La 2O 324-26%, CeO 248-52%, Nd 2O 315-17%, Pr 6O 115-7%, Sm 2O 3With Gd 2O 3Sum<2%, by weight.
6. by the catalyzer of claim 1, wherein catalyzer adds at least a alkalimetal oxide, and this oxide compound is 0.001-0.1 to the grammeatom ratio of V: 1.
7. by the catalyzer of claim 6, wherein alkalimetal oxide is the oxide compound of potassium or rubidium or caesium.
8. by the catalyzer of claim 1, wherein inorganic carrier be a kind of in annular, sphere and the garden cylindricality.
9. by the catalyzer of claim 1, wherein the particle diameter of inorganic carrier is φ 3-8mm, and porosity is 0-50%.
10. the Preparation of catalysts method of one of claim 1-9, wherein catalyzer is to prepare with spraying method.
11. catalyzer with one of claim 1-9, with the alkyl pyridine is raw material, and the corresponding cyanopyridine of gas phase ammonoxidation system is that solid catalyst is contacted with the gaseous mixture that contains alkane pyridine, ammonia, water vapour and molecule-containing keto, make alkyl change into cyano group, make cyanopyridine.
12. by the purposes of claim 11, wherein alkyl pyridine is 3-picoline or 4-picoline.
13. by the purposes of claim 11, its reaction is to carry out in fixed bed.
14. by the purposes of claim 11, wherein air speed is 1000-3000hr -1
15. by the purposes of claim 11, wherein temperature of reaction is 300 ℃-450 ℃.
16. by the purposes of claim 11, wherein alkyl pyridine concentration is 20-100g/NM 3
CN94106416A 1994-06-23 1994-06-23 Catalyst for preparing cyanopyridine by ammoxidation of alkylpyridine and its use Expired - Fee Related CN1044338C (en)

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CN1055028C (en) * 1997-01-13 2000-08-02 武汉大学 New catalyst for preparing 2,6-dichlorobenzyl nitrile by ammonia oxidation process
CN103467370B (en) * 2013-09-12 2015-07-22 南通天泽化工有限公司 Synthesis method of cyanopyridine and derivatives thereof
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
CN107537537B (en) * 2017-09-19 2020-03-06 河南省科学院高新技术研究中心 Catalyst for preparing 2-cyanopyridine by ammoxidation
CN109647467B (en) * 2017-10-12 2020-10-16 中国石油化工股份有限公司 Catalyst for oxidation of pseudocumene
CN111097464B (en) * 2018-10-25 2023-08-08 中国石油化工股份有限公司 Vanadium catalyst and preparation method thereof
CN116078371A (en) * 2022-12-30 2023-05-09 南通立洋化学有限公司 Catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof

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CN1048172A (en) * 1989-06-23 1991-01-02 标准石油公司 Maleic anhydride hydrogenation changes into tetrahydrofuran (THF) and the used coated catalysts of gamma-butyrolactone
CN1058400A (en) * 1991-08-28 1992-02-05 复旦大学 Ordinary-pressure gas-phase hydrogenating synthesis of y-j lactone with cis-anhydride

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