CN102600844A - Ni-NiO/gamma-Al2O3 catalyst for preparing pyridine and pyridine byproducts as well as preparation method - Google Patents

Abstract

The invention discloses a Ni-NiO/gamma-Al2O3 catalyst for preparing pyridine and pyridine byproducts and a preparation method. The catalyst takes gamma-Al2O3 as a carrier, the loading amount of Ni is 0.5-20% the mass of the carrier and the loading amount of NiO is 0.25-35% the mass of the carrier. The preparation method comprises the following processes of: mixing Al2O3 powder with diluted nitric acid and PEG (polyethylene glycol) 600, squeezing into strips and forming, drying and calcining to obtain the carrier gamma-Al2O3; and dissolving nickel nitrate in water, mixing with the carrier gamma-Al2O3, stirring uniformly, immersing, taking out for drying, calcining in a muffle furnace, adding to a reactor, and introducing hydrogen gas for reducing to prepare the Ni-NiO/gamma-Al2O3 catalyst for synthesizing pyridine and main pyridine byproducts. The catalyst has the advantages that the preparing equipment is simple, and the catalyst has long life; and when the catalyst is used for synthesizing pyridine and pyridine byproducts from tetrahydrofurfuryl alcohol and ammonia as raw materials, the yields are higher.

Description

Ni-NiO/ γ-the Al of preparation pyridine and accessory substance thereof 2O 3Catalyst and preparation method

Technical field

The present invention relates to a kind of Ni-NiO/ γ-Al for preparing pyridine and accessory substance thereof ₂O ₃Catalyst and preparation method belong to the catalysis and the application technology of pyridine synthesis, piperidines and isoquinolin.

Background technology

Pyridine is important organic solvent and industrial chemicals, and at medicine, agricultural chemicals has a wide range of applications in the fields such as dyestuff.

The early stage acquisition of pyridine all is the byproduct through coal tar industry or coke production, and its output is lower, and most now pyridines all are synthesized into through industry.The at present main ammonia that adopts is synthetic with the aldehydes or ketones catalytic gasification, reaches poor selectivity yet these method yields are low, and cost of material high etc. shortcoming.Through the method for tetrahydrofurfuryl alcohol and ammonia synthesis pyridine, its key technology is the efficient of catalyst.US2543424 is disclosed to be to be the raw material pyridine synthesis with tetrahydrofurfuryl alcohol, ammonia, and that it adopts is MoO ₂Or MoS ₂Load on the catalyst of aluminium oxide.US2972615 is disclosed to be to be the raw material pyridine synthesis with tetrahydrofurfuryl alcohol, ammonia, and that it adopts is V ₂O ₅Load on the catalyst of aluminium oxide.US32382214 is the raw material pyridine synthesis with tetrahydrofurfuryl alcohol, ammonia, and what it adopted is the catalyst that palladium loads on aluminium oxide.CN1736587A is the raw material pyridine synthesis with tetrahydrofurfuryl alcohol, ammonia, and that it adopts is MoO ₃Reach the oxide carried catalyst of La, Ce, Cd at aluminium oxide.CN1736588A is the raw material pyridine synthesis with tetrahydrofurfuryl alcohol, ammonia, and that it adopts is MoO ₃, V ₂O ₅Reach the oxide carried catalyst of La, Ce, Cd at aluminium oxide.All there is the short problem of the not high while catalyst life of pyridine selectivity and yield in they.

Piperidines is claimed hexahydropyridine again, is mainly used in synthetic drugs such as making local anesthetic, anodyne, and vulcanizer, epoxy curing agent, catalyst etc.It is reported that the production of domestic existing piperidines adopts Raney's nickel to make catalyst, has pyridine high pressure catalytic hydrogenation to make piperidines.The piperidines synthetic method of foreign patent introduction is to exist down with noble metal catalysts such as Ru/C/, Pd/C and Ru-Ni/C, makes piperidines with pyridine catalysis addition under 160 ℃ and the 8MPa pressure, and reaction conversion ratio is near 100%.

Isoquinolin is colourless low melting point flaky crystal, solid or liquid, and the fragrance of similar fennel oil and benzaldehyde mixture is arranged, and deposits the back color usually and can turn to be yellow.Be present in coal tar and the animal oil.Be slightly soluble in water, be dissolved in diluted acid, can with multiple immiscible organic solvent.Hoogewerff in 1885 and van Dorp have obtained sulfuric acid isoquinolin with fractionation crystallization from coal tar quinoline cut.The same year, Gabriel accomplished the synthetic of isoquinolin.Wei β gerber utilized the alkaline difference between isoquinolin and the quinoline in 1914, had developed a kind of more efficiently separation method.Industrial is raw material with coal tar crude quinoline cut mainly, produces isoquinolin by sulfonation, fractional crystallization, filtration, recrystallization, ammoniacal liquor decomposition, washing and rectifying.

Summary of the invention

The object of the present invention is to provide a kind of Ni-NiO/ γ-Al for preparing pyridine and accessory substance thereof ₂O ₃Catalyst and preparation method, it is raw material pyridine synthesis, piperidines and isoquinolin that this catalyst is used for tetrahydrofurfuryl alcohol, ammonia, and selectivity and yield with principal product pyridine are higher, and accessory substance piperidines and quinoline have higher value, the characteristics that catalyst life is long.Method for preparing catalyst is simple.

For achieving the above object, the present invention realizes through following proposal.A kind of Ni-NiO/ γ-Al for preparing pyridine and accessory substance thereof ₂O ₃Catalyst is characterized in that, this catalyst is with strip γ-Al ₂O ₃Be carrier, load group/one is Ni, and its load capacity is 0.5～20% of a carrier quality; Two of load group branch is NiO, and its load capacity is 0.25～35% of a carrier quality.

Above-mentioned Ni-NiO/ γ-Al ₂O ₃Catalyst is characterized in that, the load capacity of Ni is 1～10% of a carrier quality, and the load capacity of NiO is 5～30% of a carrier quality.

Above-mentioned Ni-NiO/ γ-Al ₂O ₃The Preparation of catalysts method is characterized in that comprising following process:

1) gathering ethanol and 80～120ml mass concentration by every milliliter is 2%～10% nitric acid and 100～120 gram Al ₂O ₃Proportion of powder is mixed, mixes, and extruded moulding, drying at room temperature after 80～150 ℃ of dryings of temperature, was warming up to 400～600 ℃ of constant temperature 4～8 hours with 8～10 ℃/min heating rate at last, obtained carrier γ-Al ₂O ₃

2) nickel nitrate is dissolved in the water, is made into the aqueous solution that mass concentration is 2～40% nickel nitrates, then according to the carrier γ-Al that makes in the aqueous solution and the step 1) ₂O ₃Volume ratio 1: (0.5～1) is mixed, is stirred, and flooded 12～48 hours; Drying at room temperature; Be 70～120 ℃ of dryings down in temperature then, at last dried presoma be warming up to 400～600 ℃ of constant temperature 4～10 hours with 8～10 ℃/min heating rate, obtain NiO/ γ-Al ₂O ₃, under 300 ℃～500 ℃, feeding hydrogen with 200ml～500ml/min, reduction 3h～8h makes the Ni-NiO/ γ-Al of pyridine synthesis and accessory substance thereof ₂O ₃Catalyst.

Advantage of the present invention: it is simple to make the catalyst device therefor, and catalyst hardness is high, and selectivity and the yield of using this catalyst institute synthetic product pyridine are higher, and accessory substance piperidines and isoquinolin have higher value, and pipeline is difficult for stopping up, and catalyst life is longer.Still has good catalytic effect behind the catalyst regeneration.

The specific embodiment

Embodiment 1

Adopt commercially available alchlor powder 100 grams; Add mass concentration and be rare nitric acid 150ml of 6%, after gathering ethanol 6008ml and mixing, be extruded into diameter then and be 3.5 centimetres bar; Drying at room temperature 3 hours; Baking is 5 hours in 150 ℃ baking oven, in Muffle furnace, is warming up to 600 ℃ of constant temperature 7 hours with 8～10 ℃/min heating rate then, obtains carrier γ-Al ₂O ₃, be cut into the strip that length is 1～3 tip of a hair.

With 33.04 gram Ni (NO ₃) ₂6H ₂O is dissolved in the 200mL water, the γ-Al of the above-mentioned strip of inciting somebody to action then ₂O ₃Carrier 100g puts into solution and mixes; Flooded 36 hours; Solution evenly is adsorbed onto in the micropore of carrier; Room temperature is placed 2 hours again 90 ℃ of dryings 3 hours, in Muffle furnace, is warming up to 450 ℃ of constant temperature with 5～8 ℃/min heating rate at last and promptly processes loaded catalyst in 5 hours, and wherein the load capacity of nickel oxide is 20% of a carrier quality.Under 350 ℃, feed hydrogen with 300ml, reduction 6h makes the Ni-NiO/ γ-Al of pyridine synthesis and accessory substance thereof ₂O ₃Catalyst, wherein the load capacity of Ni is 2% of a carrier quality, the load capacity of NiO is 18% of a carrier quality.

Embodiment 2

Carrier γ-Al ₂O ₃Making step the same with embodiment 1.

With 16.52 gram Ni (NO ₃) ₂6H ₂O is dissolved in the 200ml water, then with the γ-Al of above-mentioned strip ₂O ₃Carrier 100g puts into solution and mixes; Flooded 24 hours; Solution evenly is adsorbed onto in the micropore of carrier, and room temperature is placed 4 hours again 100 ℃ of dryings 3 hours, in Muffle furnace, is warming up to 600 ℃ of constant temperature with 12 ℃/min heating rate at last and promptly processes loaded catalyst in 5 hours.Wherein the load capacity of nickel oxide is 10% of a carrier quality.Under 450 ℃, feed hydrogen with 400ml, reduction 4h makes the Ni-NiO/ γ-Al of pyridine synthesis and accessory substance thereof ₂O ₃Catalyst, wherein the load capacity of Ni is 1% of a carrier quality, the load capacity of NiO is 9% of a carrier quality.

1%Ni-9%NiO/ γ-Al packs in the fixed bed reaction pipe ₂O ₃Catalyst 25 grams, the about 50ml of volume.The flow of raw material tetrahydrofurfuryl alcohol is 0.12mol/h, and the flow of ammonia is 1.5mol/h.Reaction temperature is 550 ℃, and reaction pressure is 1 atmospheric pressure.Collect product and carry out quantitative analysis with gas-chromatography, get the pyridine yield and reach 82.04%, the yield of piperidines reaches 6.21%, and the yield of isoquinolin reaches 8.67%.

Embodiment 3

Carrier γ-Al ₂O ₃Making step the same with embodiment 1.

With 49.55 gram Ni (NO ₃) ₂6H ₂O is dissolved in the 180ml water, then with the γ-Al of above-mentioned strip ₂O ₃Carrier 100g puts into solution and mixes; Flooded 30 hours; Solution evenly is adsorbed onto in the micropore of carrier, and after the taking-up, room temperature is placed after 3 hours 90 ℃ of dryings 2 hours again; In Muffle furnace, be warming up to 800 ℃ of constant temperature with 10 ℃/min heating rate at last and promptly processed catalyst precursor in 6 hours, the load capacity of nickel oxide is 30% of a carrier quality.Before the reaction, in reactor, feed hydrogen reducing 7h, obtain 3%Ni-27%NiO/ γ-Al ₂O ₃Catalyst.3%Ni-27%NiO/ γ-Al packs in the fixed bed reaction pipe ₂O ₃Catalyst 20g, the about 40ml of volume.The adding speed of raw material tetrahydrofurfuryl alcohol is 0.10mol/h, and the adding speed of ammonia is 1.5mol/h.Reaction temperature is 400 ℃, and reaction pressure is 1 atmospheric pressure.Collect product and carry out quantitative analysis, get the pyridine yield and reach 23.52% with gas-chromatography; The piperidines yield reaches 11.63%; The isoquinolin yield reaches 34.27%.

Claims (3)

1. Ni-NiO/ γ-Al who prepares pyridine and accessory substance thereof ₂O ₃Catalyst is characterized in that, this catalyst is with strip γ-Al ₂O ₃Be carrier, load group/one is Ni, and its load capacity is 0.5～20% of a carrier quality; Two of load group branch is NiO, and its load capacity is 0.25～35% of a carrier quality.

2. press the Ni-NiO/ γ-Al of described preparation pyridine of claim 1 and accessory substance thereof ₂O ₃Catalyst is characterized in that, the load capacity of Ni is 1～10% of a carrier quality, and the load capacity of NiO is 5～30% of a carrier quality.

3. Ni-NiO/ γ-Al who prepares described preparation pyridine of claim 1 and accessory substance thereof ₂O ₃The method of catalyst is characterized in that comprising following process:

1) gathering ethanol and 80～120ml mass concentration by every milliliter is 2%～10% nitric acid and 100～120 gram Al ₂O ₃Proportion of powder is mixed, mixes, and extruded moulding, drying at room temperature after 80～150 ℃ of dryings of temperature, was warming up to 400～600 ℃ of constant temperature 4～8 hours with 8～10 ℃/min heating rate at last, obtained carrier γ～Al ₂O ₃

2) nickel nitrate is dissolved in the water, is made into the aqueous solution that mass concentration is 2～40% nickel nitrates, then according to the carrier γ-Al that makes in the aqueous solution and the step 1) ₂O ₃Volume ratio 1: (0.5～1) is mixed, is stirred, and flooded 12～48 hours; Drying at room temperature; Be 70～120 ℃ of dryings down in temperature then, at last dried presoma be warming up to 400～600 ℃ of constant temperature 4～10 hours with 8～10 ℃/min heating rate, obtain NiO/ γ-Al ₂O ₃, under 300 ℃～500 ℃, feeding hydrogen with 200ml～500ml/min, reduction 3h～8h makes the Ni-NiO/ γ-Al of pyridine synthesis and accessory substance thereof ₂O ₃Catalyst.