CN103539736A - Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material - Google Patents

Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material Download PDF

Info

Publication number
CN103539736A
CN103539736A CN201310476359.1A CN201310476359A CN103539736A CN 103539736 A CN103539736 A CN 103539736A CN 201310476359 A CN201310476359 A CN 201310476359A CN 103539736 A CN103539736 A CN 103539736A
Authority
CN
China
Prior art keywords
cyclopentenopyridine
raw material
concentration
synthetic
nitrate
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.)
Granted
Application number
CN201310476359.1A
Other languages
Chinese (zh)
Other versions
CN103539736B (en
Inventor
俞卫华
周春晖
童东绅
任姗姗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhijiang College of ZJUT
Original Assignee
Zhijiang College of ZJUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhijiang College of ZJUT filed Critical Zhijiang College of ZJUT
Priority to CN201310476359.1A priority Critical patent/CN103539736B/en
Publication of CN103539736A publication Critical patent/CN103539736A/en
Application granted granted Critical
Publication of CN103539736B publication Critical patent/CN103539736B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a method for synthesis of 2,3-cyclopentenopyridine from glycerin as a raw material. The method is characterized in that in a fixed bed reactor, a glycerin aqueous solution having a concentration of 10-30%, cyclopentanone and ammonia gas as raw materials are synthesized into 2,3-cyclopentenopyridine in the presence of carrier gas nitrogen and catalyst gamma-alumina modified by two transition metals selected from Ti, Cu, Zn, Co and Ni at a temperature of 300-500 DEG C under normal pressure. The method has the advantages of easy acquisition of the raw materials, raw material safety, simple preparation processes, easy operation, high catalyst activity and good stability.

Description

A kind ofly take the method for glycerine as the synthetic 2,3-cyclopentenopyridine of raw material
Technical field
The present invention relates to the method for the synthetic 2,3-cyclopentenopyridine of a kind of gas-solid phase reaction, relate in particular to a kind of method of glycerine as the synthetic 2,3-cyclopentenopyridine of raw material of take.
Background technology
2,3-cyclopentenopyridine is a kind of pyridine derivate, be synthetic the 4th generation cephalosporin antibiotic cefpirome important intermediate, be also widely used in preparing plant protection product, synthetic resins, plastics etc.
At present, the preparation of 2,3-cyclopentenopyridine is mainly by the synthetic method of liquid-phase catalysis.The bibliographical information of this respect is a lot, but technological process is very complicated, and the production cycle is long, cost is high, severe reaction conditions.
Document [United States Patent (USP): 4332940,1982-06-01; Synthetic chemistry, 2008,16 (2), 242-244; Chinese patent: 201210228486.5,2012-06-30] disclose and take propenal, cyclopentanone and ammonia as raw material, the method for the synthetic 2,3-cyclopentenopyridine of gas-solid catalysis.Gas-solid catalysis technique is simple, is conducive to suitability for industrialized production, reduces costs.But along with day by day exhausting of petroleum resources and increasingly sharpening of problem of environmental pollution, the source of its raw material propylene aldehyde is restricted, because propenal mainly makes by the oxidation of oil catalytic pyrolysis product propylene.In addition, in this reaction, because of the easy inactivation of catalyzer, unavoidably need frequent handling catalyzer, and propenal has intense stimulus, toxicity is large, inflammable, volatile, and this health to stevedore has produced serious threat.Find a kind of abundant raw material again the propenal substitute of safety by gas-solid, be combined to 2,3-cyclopentenopyridine and extremely need.
Glycerine is as the by product of preparation biofuel, and due to a large amount of productions of biofuel, thereby source is abundant, low price.Glycerine is a kind of safe green renewable raw materials especially, replace propenal synthetic 2,3-cyclopenta pyridine has not only solved the safety problem that direct use propenal brings, and can reduce by 2, the price of 3-cyclopenta pyridine and subsequent product, meanwhile, to effectively making full use of of biological diesel oil byproduct glycerin, be conducive to the Sustainable development of Biodiesel.Therefore, take glycerine as the synthetic 2,3-cyclopentenopyridine of raw material is the production technique of an economy and environmental protection, yet the catalyzer matching with it and catalysis synthesizing technology are current, do not have to report accordingly.
Summary of the invention
The object of this invention is to provide and a kind ofly take glycerine, cyclopentanone and ammonia and be the method for raw material synthetic 2,3-cyclopentenopyridine in fixed-bed reactor, to overcome the above-mentioned problem existing.
The technical solution used in the present invention is:
First, prepare a kind of modified aluminas as the catalyzer that catalyzes and synthesizes 2,3-cyclopentano pyridine, this modified oxidized dose adopts pickling process preparation, and dipping is divided into twice:
1, flood for the first time, prepare the γ-Al of titaniferous 2o 3(Ti/ γ-Al 2o 3).With spherical gamma-Al 2o 3for carrier, the steeping fluid of the titaniferous preparing is added to γ-Al 2o 3, through 12-24h dipping, in 80-120 ℃ of dry 4-8h, naturally cooling, obtains head product, and this head product is described as Ti/ γ-Al 2o 3.Wherein, described spherical gamma-Al 2o 3particle diameter 2-3mm, mean pore size 5-7nn, specific surface area 100-250m 2/ g, pore volume is 0.5-0.7ml/g; Described titaniferous steeping fluid is the ethanolic soln of titanium tetrachloride, titanium ethanolate, isopropyl titanate or butyl (tetra) titanate, and concentration is 3.5-33%.Preferably, the concentration of described titanium tetrachloride ethanolic soln is 3.5-20.9%, titanium tetrachloride, γ-Al 2o 3with the mass ratio of ethanol be 1:4.8-25.0:3.8-27.7; The concentration of titanium ethanolate ethanolic soln is 4.2-24.1%, titanium ethanolate, γ-Al 2o 3with the mass ratio of ethanol be 1:4.0-20.8:3.2-23.0; The concentration of isopropyl titanate ethanolic soln is 5.1-28.3%, isopropyl titanate, γ-Al 2o 3with the mass ratio of ethanol be 1:3.2-16.7:2.5-18.5; The concentration of butyl (tetra) titanate ethanolic soln is 6.1-32.1%, butyl (tetra) titanate, γ-Al 2o 3with the mass ratio of ethanol be 1:2.7-14.0:2.1-15.4.
2, flood for the second time, preparation is containing the Ti/ γ-Al of transition metal M 2o 3(M/Ti/ γ-Al 2o 3).The dipping solution for the second time containing the transition metal M outside Ti preparing is sprayed onto to the Ti/ γ-Al preparing as stated above 2o 3, after 12-24h dipping, in 80-120 ℃ of dry, 450～600 ℃ of roastings, making modified aluminas, modified aluminas is described as M/Ti/ γ-Al 2o 3, the total mass per-cent of transition metal is γ-Al 2o 3the 2-6% of quality.Preferably, described transition metal M is a kind of in zinc, copper, cobalt, nickel, and described steeping fluid is for the second time the aqueous solution of cupric nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or nickelous nitrate.More excellent, the concentration of described copper nitrate aqueous solution is 5.2-28.4%, cupric nitrate, γ-Al 2o 3with the mass ratio of water be 1:5.0-26.2:2.5-18.4; The concentration of zinc nitrate aqueous solution is 6.2-32.4%, zinc nitrate, γ-Al 2o 3with the mass ratio of water be 1:4.2-21.8:2.1-15.2; The concentration of the aqueous solution of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 5.8-30.8%, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, γ-Al 2o 3with the mass ratio of water be 1:4.5-23.4:2.2-16.4; The concentration of the aqueous solution of nickelous nitrate is 6.7-34.3%, nickelous nitrate, γ-Al 2o 3with the mass ratio of water be 1:3.8-20.0:1.9-14.0.
3, the modified aluminas M/Ti/ γ-Al being prepared by aforesaid method 2o 3catalysis gas-solid phase reaction synthesizes 2,3-cyclopentenopyridine, and concrete grammar is: raw material aqueous glycerin solution, cyclopentanone and ammonia and carrier gas nitrogen are passed into modified alumina catalyst M/Ti/ γ-Al is housed 2o 3fixed-bed reactor, wherein, the mass concentration of glycerine is 10～30%, is technical grade pure glycerin or biodiesel byproduct crude glycerin; The feeding liquid hourly space velocity of aqueous glycerin solution is 0.10～1.00h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.05～0.15h -1, ammonia air speed is 50-150h -1, nitrogen air speed is 1000-2500h -1, under normal pressure (standard atmospheric pressure) and 300～500 ℃ of conditions, reacting, synthetic gas obtains mixture through condensation, and mixture, through fractionation by distillation, obtains 2,3-cyclopentenopyridine.
Synthetic method of the present invention has following remarkable advantage:
(1) in the present invention, with glycerine, replace conventional propenal, guaranteeing under the prerequisite of synthetic ratio, because reaction raw materials glycerine is cheap and easy to get, both can adopt technical grade pure glycerin, also can adopt the raw glycerine of biodiesel byproduct, especially solved the excessive problem of by-product glycerol of biological diesel oil, ensured the Sustainable development of whole industrial chain, be conducive to the Sustainable development of Biodiesel, thereby greatly reduce 2, the price of 3-cyclopenta pyridine and subsequent product, whole building-up process economy and environmental protection, production technique is cheap and easy to get, thereby easier promotion and application,
(2) the present invention adopts twice pickling process to prepare modified aluminas, now spherical gamma-Al 2o 3ti/ γ-the Al of upper formation titaniferous 2o 3, after oven dry, carry out again double-steeping, at Ti/ γ-Al 2o 3on carry out the second transition metal dipping form M/Ti/ γ-Al 2o 3in aluminium oxide structure, exist B acid, L sour, can affect its activity and stability, therefore in the present invention, the selected transition metal of steeping process can be adjusted indexs such as the B acid of aluminum oxide and L acid, total acid content and strength of acid, thereby support of the catalyst provided by the invention is easy to get, preparation method is simple, easy handling, catalyst activity is high, good stability.When this modified alumina catalyst is applied to 2,3-cyclopentenopyridine, take glycerine, cyclopentanone and ammonia as raw material synthetic 2, the gas-solid phase reaction of 3-cyclopenta pyridine, obtains good effect, catalyzer low price, reaction is easily implemented, and reaction conditions is gentle, has good DEVELOPMENT PROSPECT.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
First 1.6132 g titanium tetrachlorides and 19.3 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.61ml/g), naturally cooling after 12h dipping, 80 ℃ of dry 4h, obtains 2%Ti/ γ-Al 2o 3; Again by 2.3351g Cu (NO 3) 23H 2the steeping fluid that O and 12.2 g water are hybridly prepared into adds 2%Ti/ γ-Al 2o 3in, after 12h dipping, 80 ℃ of dry 4h, 500 ℃ of roastings make modified alumina catalyst 3%Cu/2%Ti/ γ-Al 2o 3; Finally, the reaction for the synthesis of 2,3-cyclopentenopyridine by this modified alumina catalyst: raw material aqueous glycerin solution (mass concentration is 15%), cyclopentanone and ammonia and carrier gas nitrogen are passed into modified alumina catalyst 3%Cu/2%Ti/ γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.23h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.07h -1, ammonia air speed is 54.0h -1, nitrogen air speed is 1066.3h -1, while reacting under normal pressure and 300 ℃ of conditions, the transformation efficiency of glycerine is 70.3%, the selectivity of 2,3-cyclopentenopyridine is 81.6%.
Adopt the present embodiment processing condition, reaction raw materials glycerine is cheap and easy to get, both can adopt technical grade pure glycerin, also can adopt the raw glycerine of biodiesel byproduct, solve the excessive problem of by-product glycerol of biological diesel oil, ensured the Sustainable development of whole industrial chain; And modified alumina catalyst carrier is easy to get, preparation method is simple, easy handling, and catalyst activity is high, good stability.It is the gas-solid phase reaction of the synthetic 2,3-cyclopentenopyridine of raw material that this modified alumina catalyst is used for take glycerine, cyclopentanone and ammonia, obtains good effect, catalyzer low price, and reaction is easily implemented, and reaction conditions is gentle, has good DEVELOPMENT PROSPECT.
Embodiment 2:
The principle of work of the present embodiment and work flow are identical with arranging of embodiment 1, and difference is: first 2.9401 titanium ethanolates and 19.3 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.61ml/g), through 12h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 3%Ti/ γ-Al 2o 3; Again by 1.5408 g Cu (NO 3) 23H 2the steeping fluid for the second time that O and 12.2 g water are hybridly prepared into adds 3%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 500 ℃ of roastings make modified alumina catalyst 2%Cu/3%Ti/ γ-Al 2o 3; Finally by this modified alumina catalyst 2%Cu/3%Ti/ γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration is 20%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 2%Cu/3%Ti/ γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.49h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.09h -1, ammonia air speed is 78.7h -1, nitrogen air speed is 1777.2h -1, while reacting under normal pressure and 350 ℃ of conditions, the transformation efficiency of glycerine is 72.5%, the selectivity of 2,3-cyclopentenopyridine is 84.3%.
Embodiment 3:
The principle of work of the present embodiment and flow process are identical with arranging of embodiment 1, and difference is: first 2.4167 g isopropyl titanates and 19.3 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.61ml/g), through 12h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 2%Ti/ γ-Al 2o 3; Again by 3.7906 g Zn (NO 3) 26H 2the steeping fluid for the second time that O and 12.2 g water are hybridly prepared into adds 2%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 500 ℃ of roastings make modified alumina catalyst 4%Zn/2%Ti/ γ-Al 2o 3; Finally, by this modified alumina catalyst 4%Zn/2%Ti/ γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration 18%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 4%Zn/2%Ti/ γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.90h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.11h -1, ammonia air speed is 107.9h -1, nitrogen air speed is 1954.9 h -1, while reacting under normal pressure and 380 ℃ of conditions, the transformation efficiency of glycerine is 74.9%, the selectivity of 2,3-cyclopentenopyridine is 75.5%.
Embodiment 4:
The principle of work of the present embodiment and flow process are identical with arranging of embodiment 1, and difference is: first 4.3861 g butyl (tetra) titanates and 19.3 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.61ml/g), through 12h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 3%Ti/ γ-Al 2o 3; Again by 2.8137g Zn (NO 3) 26H 2the steeping fluid for the second time that O and 12.2 g water are hybridly prepared into adds 3%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 500 ℃ of roastings make modified alumina catalyst 3%Zn/3%Ti/ γ-Al 2o 3; Finally, by this modified alumina catalyst 3%Zn/3%Ti/ γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration 20%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 3%Zn/3%Ti/ γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 1.0h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.14h -1, ammonia air speed is 143.9h -1, nitrogen air speed is 2132.6 h -1, while reacting under normal pressure and 400 ℃ of conditions, the transformation efficiency of glycerine is 80.2%; The selectivity of 2,3-cyclopentenopyridine is 70.4%.
Embodiment 5:
The principle of work of the present embodiment and flow process are identical with arranging of embodiment 1, and difference is: first 2.4447 g titanium tetrachlorides and 17.7 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.56ml/g), through 20h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 3%Ti/ γ-Al 2o 3; Again by 1.7261 g Co (NO 3) 26H 2the steeping fluid for the second time that O and 11.2 g water are hybridly prepared into adds 3%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 550 ℃ of roastings make modified alumina catalyst 2%Co/3%Ti/ γ-Al 2o 3; Finally, by this modified alumina catalyst 2%Co/3%Ti/ γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration 15%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 2%Co/3%Ti/ γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.23h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.07h -1, ammonia air speed is 54.0h -1, nitrogen air speed is 1599.5h -1, while reacting under normal pressure and 350 ℃ of conditions, the transformation efficiency of glycerine is 68.8%, the selectivity of 2,3-cyclopentenopyridine is 75.3%.
Embodiment 6:
The principle of work of the present embodiment and flow process are identical with arranging of embodiment 1, and difference is: first 3.9609 g titanium ethanolates and 17.7 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.56ml/g), through 20h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 4%Ti/ γ-Al 2o 3; Again by 1.7261 g Co (NO 3) 26H 2the steeping fluid for the second time that O and 11.2 g water are hybridly prepared into adds 4%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 550 ℃ of roastings make modified alumina catalyst 2%Co/4%Ti/ γ-Al 2o 3.Then, by this modified alumina catalyst 2%Co/4%Ti/ γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration 20%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 2%Co/4%Ti/ γ-Al is housed 2o 3.Fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.66h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.09h -1, ammonia air speed is 78.7h -1, nitrogen air speed is 1777.2h -1, while reacting under normal pressure and 380 ℃ of conditions, the transformation efficiency of glycerine is 72.6%; The selectivity of 2,3-cyclopentenopyridine is 77.8%.
Embodiment 7:
The principle of work of the present embodiment and flow process are identical with arranging of embodiment 1, and difference is: first 6.2325 g isopropyl titanates and 21.2 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.67ml/g), through 20h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 5%Ti/ γ-Al 2o 3; Again by 1.0008 g Ni (NO 3) 26H 2the steeping fluid for the second time that O and 13.4 g water are hybridly prepared into adds 5%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 550 ℃ of roastings make modified alumina catalyst 1%Ni/5%Ti-γ-Al 2o 3; Finally, by this modified alumina catalyst 1%Ni/5%Ti-γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration 25%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 1%Ni/5%Ti-γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.54h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.11h -1, ammonia air speed is 107.9h -1, nitrogen air speed is 1954.9h -1, while reacting under normal pressure and 400 ℃ of conditions, the transformation efficiency of glycerine is 82.7%; The selectivity of 2,3-cyclopentenopyridine is 66.5%.
Embodiment 8:
The principle of work of the present embodiment and flow process are identical with arranging of embodiment 1, and difference is: first 2.4447g titanium tetrachloride and 21.2 g ethanol are hybridly prepared into titaniferous steeping fluid, this titaniferous steeping fluid is added to 20g γ-Al 2o 3in (pore volume 0.67ml/g), through 20h dipping, after 80 ℃ of dry 4h, naturally cooling obtains 3%Ti/ γ-Al 2o 3; Again by 3.0644g Ni (NO 3) 26H 2the steeping fluid for the second time that O and 13.4 g water are hybridly prepared into adds 3%Ti/ γ-Al 2o 3in, through 12h dipping, after 80 ℃ of dry 4h, 500 ℃ of roastings make modified alumina catalyst 3%Ni/3%Ti-γ-Al 2o 3; Finally, by this modified alumina catalyst 3%Ni/3%Ti-γ-Al 2o 3reaction for the synthesis of 2,3-cyclopentenopyridine: raw material aqueous glycerin solution (mass concentration 30%), cyclopentanone and ammonia and carrier gas nitrogen are passed into this modified alumina catalyst 3%Ni/3%Ti-γ-Al is housed 2o 3fixed-bed reactor, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.53h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.12h -1, ammonia air speed is 125.9h -1, nitrogen air speed is 2132.6h -1, while reacting under normal pressure and 450 ℃ of conditions, the transformation efficiency of glycerine is 86.4%, the selectivity of 2,3-cyclopentenopyridine is 63.9%.

Claims (9)

1. take glycerine as raw material synthetic 2 for one kind, the method of 3-cyclopenta pyridine, it is characterized in that: this building-up reactions be take modified aluminas as catalyzer, take aqueous glycerin solution, cyclopentanone and ammonia as raw material, nitrogen is carrier gas, under 300～500 ℃ and condition of normal pressure, above-mentioned raw materials to be sent in the fixed-bed reactor that modified aluminas is housed and reacted by carrier gas, the feeding liquid hourly space velocity of aqueous glycerin solution is 0.10～1.00h -1, the feeding liquid hourly space velocity of cyclopentanone is 0.05～0.15h -1, ammonia air speed is 50-150h -1, nitrogen air speed is 1000-2500h -1, synthetic gained gas obtains mixture through condensation, and mixture, through fractionation by distillation, obtains 2,3-cyclopentenopyridine.
2. as claimed in claim 1ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: described aqueous glycerin solution is technical grade pure glycerin or biodiesel byproduct crude glycerin, its mass concentration is 10～30%.
3. as claimed in claim 1ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: described modified alumina catalyst adopts pickling process preparation, and dipping is divided into twice, with spherical gamma-Al 2o 3for carrier, by γ-Al 2o 3join the titaniferous steeping fluid preparing, after 12-24h dipping, after 80-120 ℃ of dry 4-8h, obtain head product, this head product is described as Ti/ γ-Al 2o 3, then the steeping fluid for the second time containing the transition metal M except Ti preparing is sprayed onto to Ti/ γ-Al 2o 3upper, after 12-24h dipping, in 80-120 ℃ of dry, 450～600 ℃ of roastings, make modified aluminas, modified aluminas is described as M/Ti/ γ-Al 2o 3, in modified aluminas, the total mass per-cent of transition metal accounts for γ-Al 2o 3the 2-6% of quality.
4. as claimed in claim 3ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: described titaniferous steeping fluid is the ethanolic soln of titanium tetrachloride, titanium ethanolate, isopropyl titanate or butyl (tetra) titanate, concentration is 3.5-33%.
5. as claimed in claim 3ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: described transition metal M is zinc, copper, cobalt, nickel.
6. as claimed in claim 4ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: the concentration of described titanium tetrachloride ethanolic soln is 3.5-20.9%, titanium tetrachloride, γ-Al 2o 3with the mass ratio of ethanol be 1:4.8-25.0:3.8-27.7; The concentration of titanium ethanolate ethanolic soln is 4.2-24.1%, titanium ethanolate, γ-Al 2o 3with the mass ratio of ethanol be 1:4.0-20.8:3.2-23.0; The concentration of isopropyl titanate ethanolic soln is 5.1-28.3%, isopropyl titanate, γ-Al 2o 3with the mass ratio of ethanol be 1:3.2-16.7:2.5-18.5; The concentration of butyl (tetra) titanate ethanolic soln is 6.1-32.1%, butyl (tetra) titanate, γ-Al 2o 3with the mass ratio of ethanol be 1:2.7-14.0:2.1-15.4.
A kind of as described in claim 3-6 any one to take glycerine be the method for the synthetic 2,3-cyclopentenopyridine of raw material, it is characterized in that: described steeping fluid is for the second time the aqueous solution of cupric nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or nickelous nitrate, its concentration is 5-35%.
8. as claimed in claim 7ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: the concentration of described copper nitrate aqueous solution is 5.2-28.4%, cupric nitrate, γ-Al 2o 3with the mass ratio of water be 1:5.0-26.2:2.5-18.4; The concentration of zinc nitrate aqueous solution is 6.2-32.4%, zinc nitrate, γ-Al 2o 3with the mass ratio of water be 1:4.2-21.8:2.1-15.2; The concentration of the aqueous solution of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is 5.8-30.8%, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, γ-Al 2o 3with the mass ratio of water be 1:4.5-23.4:2.2-16.4; The concentration of the aqueous solution of nickelous nitrate is 6.7-34.3%, nickelous nitrate, γ-Al 2o 3with the mass ratio of water be 1:3.8-20.0:1.9-14.0.
9. as claimed in claim 3ly a kind ofly take glycerine and be to it is characterized in that the method for the synthetic 2,3-cyclopentenopyridine of raw material: described spherical gamma-Al 2o 3particle diameter 2-3mm, mean pore size 5-7nn, specific surface area 100-250m 2/ g, pore volume is 0.5-0.7ml/g.
CN201310476359.1A 2013-10-14 2013-10-14 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material Expired - Fee Related CN103539736B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310476359.1A CN103539736B (en) 2013-10-14 2013-10-14 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310476359.1A CN103539736B (en) 2013-10-14 2013-10-14 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material

Publications (2)

Publication Number Publication Date
CN103539736A true CN103539736A (en) 2014-01-29
CN103539736B CN103539736B (en) 2015-05-13

Family

ID=49963642

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310476359.1A Expired - Fee Related CN103539736B (en) 2013-10-14 2013-10-14 Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material

Country Status (1)

Country Link
CN (1) CN103539736B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109663592A (en) * 2017-10-13 2019-04-23 中国石油化工股份有限公司 High-carbon binary ester through hydrogenation prepares high-carbon dihydric alcohol catalyst
CN116351410A (en) * 2023-03-20 2023-06-30 浙江工业大学之江学院 Solid acid catalyst loaded with ternary metal oxides of titanium, vanadium and cerium, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332940A (en) * 1976-09-03 1982-06-01 Deutsche Gold -Und Silber-Scheideanstalt Vormals Roessler Process for the production of 2,3-cycloalkenopyridines
CN1907973A (en) * 2006-08-22 2007-02-07 济南诚汇双达化工有限公司 Process for preparing 2,3-cyclopentene pyridine
CN102744056A (en) * 2012-06-30 2012-10-24 浙江工业大学 Ti-V loaded aluminum-pillared montmorillonite heterogeneous catalyst and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4332940A (en) * 1976-09-03 1982-06-01 Deutsche Gold -Und Silber-Scheideanstalt Vormals Roessler Process for the production of 2,3-cycloalkenopyridines
CN1907973A (en) * 2006-08-22 2007-02-07 济南诚汇双达化工有限公司 Process for preparing 2,3-cyclopentene pyridine
CN102744056A (en) * 2012-06-30 2012-10-24 浙江工业大学 Ti-V loaded aluminum-pillared montmorillonite heterogeneous catalyst and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
吴梁鹏，等: "甘油制备丙烯醛的最新研究进展", 《现代化工》 *
魏昭彬，等: "2,3-环戊烯并吡啶的多相催化合成", 《合成化学》 *
黄士学，等: "甘油脱水制丙烯醛催化剂的研究进展", 《化工进展》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109663592A (en) * 2017-10-13 2019-04-23 中国石油化工股份有限公司 High-carbon binary ester through hydrogenation prepares high-carbon dihydric alcohol catalyst
CN109663592B (en) * 2017-10-13 2022-02-22 中国石油化工股份有限公司 Catalyst for preparing high-carbon dihydric alcohol by hydrogenation of high-carbon dibasic ester
CN116351410A (en) * 2023-03-20 2023-06-30 浙江工业大学之江学院 Solid acid catalyst loaded with ternary metal oxides of titanium, vanadium and cerium, and preparation method and application thereof
CN116351410B (en) * 2023-03-20 2024-04-16 浙江工业大学之江学院 Solid acid catalyst loaded with ternary metal oxides of titanium, vanadium and cerium, and preparation method and application thereof

Also Published As

Publication number Publication date
CN103539736B (en) 2015-05-13

Similar Documents

Publication Publication Date Title
CN102146019B (en) Method for preparing alcohols from olefin
CN102603681B (en) Method for preparing furfuryl alcohol through furfural liquid-phase catalytic hydrogenation
CN100432034C (en) Method of continuously preparing 1,2-dihydroxypropane by glycerin catalytic hydrogenation
CN106673962B (en) A kind of preparation method of isopropanol
CN105130746A (en) Method for producing pentanediol through selective hydrogenolysis of furan derivative
CN102432565B (en) Method for preparing 2-hydroxyethylpiperazine
CN103433043B (en) High-selectivity catalyst for preparing phthalide by hydrogenation of phthalic anhydride
CN104785261A (en) Oxalate hydrogenation catalyst synthesized by mixed silicon source method and preparation method thereof
CN103539736B (en) Method for synthesis of 2,3-cyclopentenopyridine from glycerin as raw material
CN103641836A (en) Preparation method of 2-methyl triethylene diamine
CN104387340A (en) Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine
CN104525192A (en) Method for preparing catalyst used in preparation of cyclohexene by virtue of selective hydrogenation of benzene
CN103240095A (en) Methyl acetate hydrogenation catalyst and preparation method thereof
CN110368949A (en) A kind of CO adds hydrogen low-carbon alcohols GaFe base catalyst and preparation method and application
CN103157490B (en) Catalyst for producing ethanol by hydrogenation of acetic ester, and preparation method thereof
CN102649062A (en) Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation
CN104761443A (en) A method of continuously preparing 3,5,5-trimethyl-3-cyclohexene-1-one
CN105384616A (en) Synthetic method for methoxyacetone
CN102527426A (en) Preparation method for catalyst for preparing ethylene by dehydrating ethanol
CN104549339A (en) Methane selective oxidation catalyst, as well as preparation method and application thereof
CN102649746A (en) Method for producing glycolic acid ester through adding hydrogen in oxalic ester
CN106513001B (en) It is a kind of by the catalyst and preparation method of synthesis gas synthesizing alcohol and application
CN103242175A (en) Preparation method of monoethanol diisopropanolamine
WO2009151021A1 (en) Method for producing propylene glycol
CN107445839A (en) The synthetic method of glyoxylic ester

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150513

Termination date: 20201014