CN116078371A - Catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof - Google Patents
Catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof Download PDFInfo
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- CN116078371A CN116078371A CN202211728201.4A CN202211728201A CN116078371A CN 116078371 A CN116078371 A CN 116078371A CN 202211728201 A CN202211728201 A CN 202211728201A CN 116078371 A CN116078371 A CN 116078371A
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- Prior art keywords
- catalyst
- cyanopyridine
- mesoporous carbon
- ammoxidation
- tin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010902 straw Substances 0.000 claims abstract description 10
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000007833 carbon precursor Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010981 drying operation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- NQQVFXUMIDALNH-UHFFFAOYSA-N picloram Chemical compound NC1=C(Cl)C(Cl)=NC(C(O)=O)=C1Cl NQQVFXUMIDALNH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000005595 Picloram Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- GHFGOVUYCKZOJH-UHFFFAOYSA-N pyridine-2,3-dicarbonitrile Chemical compound N#CC1=CC=CN=C1C#N GHFGOVUYCKZOJH-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical group [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalytic synthesis, and particularly relates to a catalyst for preparing 2-cyanopyridine by catalytic ammoxidation and application thereof. According to the invention, mesoporous carbon is selected as a carrier, and tin dioxide and antimonous oxide with specific proportions are loaded, so that the ammoxidation catalyst with high catalytic activity is obtained. The tin-antimony mesoporous carbon catalyst has high specific surface area and porosity, high catalytic activity and efficiency, can be recycled for multiple times, has long service life, can keep excellent catalytic performance by only using two active metal raw materials, has simple preparation process and reduces cost. The invention uses the waste straw to prepare the mesoporous carbon, is environment-friendly, and has high porosity and strong adsorption capacity to active metals. When the tin-antimony mesoporous carbon catalyst is used for preparing 2-cyanopyridine by catalytic ammoxidation, the conversion rate of raw materials is more than 99.9%, the selectivity of 2-cyanopyridine is more than 90%, and the yield is more than or equal to 90%, so that the catalyst has great industrial value.
Description
Technical Field
The invention relates to the technical field of catalytic synthesis, in particular to the field of IPC (industrial personal computer) classification number B01J 27/19, and more particularly relates to a catalyst for preparing 2-cyanopyridine by catalyzing ammoxidation reaction and application thereof.
Background
2-cyanopyridine is an important intermediate in fine organic synthesis, and is widely used in the production of fine organic chemicals such as various medicines, pesticides and dyes, for example, the synthesis of agricultural herbicide 4-amino-3, 5, 6-trichloropyridine-2-carboxylic acid (picloram) and the Xa factor inhibitor betrocoban are all independent of 2-cyanopyridine. In the preparation process method of the 2-cyanopyridine, the 2-picoline catalytic ammoxidation method is widely applied in actual production due to the characteristics of sufficient raw material sources, no relation to high-toxic cyanide, relatively low product preparation cost and the like. However, the ammoxidation reaction is a complicated process, and there are many side reactions other than the main reaction, which greatly reduces the yield of dicyanopyridine. Therefore, research on a novel catalyst with good selectivity and high conversion rate, optimization of process conditions and reduction of production cost are key to the technology of synthesizing 2-cyanopyridine by ammoxidation.
At present, the catalyst for synthesizing cyanopyridine by catalyzing ammoxidation reaction is mostly prepared by an impregnation method, namely an equal volume impregnation method, namely adding a solution which is enough to fill the pore volume of the carrier particles or slightly less, and carrying the solution on a porous carrier. For a powdered support, the impregnation fluid volume needs to be slightly larger than the pore volume (known as wet impregnation) unless the catalyst precursor is strongly adsorbed on the support. In particular, during drying, continuous stirring of the slurry is important in order to ensure uniform distribution of the catalyst precursor on the support. The carrier commonly used in the prior art is titanium dioxide.
The main component of the ammoxidation catalyst used in the prior art is V, cr, P, tiO2 = 10-30%, 0-1%, 70-90%, the conversion rate of 2-methylpyridine is only more than 98%, the selectivity of 2-cyanopyridine is more than 88%, and the yield is more than or equal to 82%; the catalytic active part in the catalyst is a plurality of metal compounds, the process is complex, the catalytic efficiency is low, and the byproducts are more. The prior art CN103467370B discloses a method for synthesizing cyanopyridine, wherein the used catalyst is a vanadium-titanium catalyst, a plurality of metal compounds are needed for preparation, the cost is high, the method is not environment-friendly, the efficiency of preparing 2-cyanopyridine by catalyzing 2-picoline ammoxidation is low, and the yield is only about 70-80%.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalyst for preparing 2-cyanopyridine by catalyzing ammoxidation reaction, which has high activity, high raw material conversion rate, high product selectivity, high yield, long service life, simple production process and environment friendliness.
In another aspect, the invention also aims to provide an application of the catalyst for preparing 2-cyanopyridine by catalyzing ammoxidation.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the catalyst for preparing 2-cyanopyridine by catalytic ammoxidation is characterized by being a tin-antimony mesoporous carbon catalyst and prepared by the following method:
mesoporous carbon is added into a mixed solution of tin dioxide and antimonous oxide, and after stirring and mixing uniformly, the mesoporous carbon catalyst is obtained after drying, calcining, acid leaching treatment, water washing, filtering and drying.
Preferably, the concentration of the tin dioxide in the mixed solution of the tin dioxide and the antimonous oxide is 0.04-0.07 g/mL, and the concentration of the antimonous oxide is 0.02-0.05 g/mL.
Preferably, the stirring time for stirring and uniformly mixing is 1-3 h;
preferably, the drying operation is that stirring is carried out at 70-100 ℃ until the mixture is dried, and then drying is carried out at 110-130 ℃;
preferably, the temperature-raising program of the calcination is to raise the temperature to 800-1000 ℃ at the speed of 2-5 ℃/min, and then preserving the heat for 2-5 h.
Preferably, the acid used in the acid leaching treatment is dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid; further preferably, the mass concentration of the dilute hydrochloric acid is 5%.
Preferably, the acid leaching treatment is carried out by immersing and vibrating the calcined product in acid to remove impurities.
Preferably, the mass fraction of tin element in the catalyst is 20-30%, and the mass fraction of antimony element is 25-35%.
Preferably, the specific surface area of the catalyst is 850-1200 m 2 /g。
Preferably, the pore diameter of the catalyst is 5.5-10.8 nm.
According to the invention, mesoporous carbon is selected as a carrier, and tin dioxide and antimonous oxide with specific proportions are loaded, so that the ammoxidation catalyst with high catalytic activity is obtained. The invention creatively discovers the excellent catalytic activity of tin-antimony active bimetallic on ammoxidation reaction, and obviously improves the conversion rate of 2-picoline raw material and the selectivity of 2-cyanopyridine product. The inventor also finds that the improvement of the tin-antimony loading in the catalyst is beneficial to improving the product yield within a certain range, and especially when the tin loading is 25 percent and the antimony loading is 30 percent, the yield of the 2-cyanopyridine prepared by the catalytic ammoxidation reaction can reach 90.8 percent; however, when the tin loading exceeds 30% and the antimony loading exceeds 35%, the yield of the product is rather lowered, and the inventors speculate that the reduction in the specific surface area of the catalyst due to the excessively high loading may be caused by the increase in the pore diameter, resulting in the decrease in the effective surface area and the corresponding decrease in the catalytic efficiency. The invention increases the effective surface area of the catalyst by specifically limiting the calcination procedure and the acid leaching treatment method in the catalyst preparation process and adjusting the loading amount of active metal, thereby improving the catalytic activity and the service life of the catalyst.
Preferably, the mesoporous carbon is prepared by the steps of:
s1: mixing straw with inorganic acid for reaction, filtering, adding alkali solution for activation, and drying to obtain mesoporous carbon precursor;
s2: calcining the mesoporous carbon precursor under the protection of inert gas, soaking the calcined mesoporous carbon precursor in strong acid, removing impurities, washing with water, and drying to obtain the mesoporous carbon.
Preferably, the straw is a sheared waste straw;
preferably, the inorganic acid is dilute hydrochloric acid, dilute sulfuric acid or dilute nitric acid;
preferably, the reaction time is 10 to 15 hours;
preferably, the alkali solution is sodium hydroxide solution or potassium hydroxide solution;
preferably, the drying operation in the step S1 is that stirring is carried out at 70-100 ℃ until the mixture is dried, and then drying is carried out at 110-130 ℃;
preferably, the inert gas is nitrogen or argon;
preferably, the temperature rise program of the calcination in the step S2 is to raise the temperature to 500-700 ℃ at a speed of 1-3 ℃/min, and then preserving the temperature for 2-5 h.
Preferably, the strong acid is hydrofluoric acid, hypochlorous acid, hydrochloric acid or sulfuric acid; further preferably, the strong acid is 10wt% hydrofluoric acid.
The invention selects the waste straw as the material for preparing the mesoporous carbon, realizes waste utilization, has sufficient raw materials, can carry out mass production, reduces the cost and meets the requirements of green chemical industry. In addition, the invention carries out pre-carbonization treatment on the straw by acid and alkali, so that the fiber of the straw is broken, the time required by calcination and carbonization can be shortened, and the temperature required by calcination can be reduced. The inventor also finds that mesoporous carbon without removing impurities has larger difference on the adsorptivity of active metals, and the concentration and the type of acid, the calcining temperature and the drying operation in the preparation process all have influence on the impurity removal of the mesoporous carbon. In addition, in consideration of the fact that the mesoporous carbon powder is easy to agglomerate when being directly dried at a high temperature, the mesoporous carbon powder is stirred to be dry at a lower temperature before being dried, and the operation is also beneficial to obtaining a higher specific surface area.
In another aspect, the invention provides an application of the catalyst for preparing 2-cyanopyridine by catalytic ammoxidation, which is applied to preparing 2-cyanopyridine by catalytic ammoxidation of 2-picoline.
Preferably, the step of ammoxidation of 2-picoline to produce 2-cyanopyridine comprises: filling the catalyst in a tubular fixed bed reactor, adding 2-methylpyridine and ammonia water, introducing oxygen-containing gas and ammonia gas, reacting to obtain reaction gas, condensing the reaction gas, layering, and rectifying to obtain the finished product 2-cyanopyridine.
Preferably, the molar ratio of the oxygen-containing gas, the 2-picoline, the ammonia gas and the ammonia water is 200-300: 1-2: 40-60: 0.5 to 2; further preferably, 245:1.1:54:1;
preferably, the oxygen-containing gas is air.
Preferably, the filling amount of the catalyst is 800-1200 mL; further preferably 1000mL.
Preferably, after the catalyst is filled in the tubular fixed bed reactor, the temperature is raised to 350-400 ℃;
preferably, the preheating temperature of the 2-picoline, the ammonia water, the oxygen-containing gas and the ammonia gas before entering the reactor is 220-230 ℃;
preferably, the specific operation of the layering is layering by a layering kettle, and the residence time of the crude 2-cyanopyridine at the lower layer in the layering kettle is controlled to be 20-30 min.
Compared with the prior art, the invention has the following beneficial effects:
1. the tin-antimony mesoporous carbon catalyst has high specific surface area and porosity, high catalytic activity and efficiency, can be recycled for multiple times, and has long service life;
2. the tin-antimony mesoporous carbon catalyst only needs two active metal raw materials, has simple preparation process and lower cost, and can still maintain excellent catalytic performance;
3. the mesoporous carbon used by the tin-antimony mesoporous carbon catalyst is prepared by taking waste straws as raw materials, and is utilized by waste, green and environment-friendly, and suitable for industrial production;
4. the mesoporous carbon prepared by the method has high porosity and strong adsorption capacity to active metals, and the raw material utilization rate is high when the tin-antimony mesoporous carbon catalyst is prepared, and the high-content active metals can be loaded, so that the catalyst consumption is reduced;
5. when the tin-antimony mesoporous carbon catalyst is used for preparing 2-cyanopyridine by catalytic ammoxidation, the conversion rate of raw material 2-picoline is more than 99.9%, the selectivity of 2-cyanopyridine is more than 90%, the yield is more than or equal to 90%, the cost can be effectively saved, and the method has great industrialization value.
Detailed Description
Example 1
The embodiment provides a catalyst for preparing 2-cyanopyridine by catalytic ammoxidation, wherein the catalyst is a tin-antimony mesoporous carbon catalyst and is prepared by the following method:
preparing a mixed solution of tin dioxide and antimony trioxide by 200ml of deionized water, 8.4g of tin dioxide and 5g of antimony trioxide; 10.0g of mesoporous carbon is added into the mixed solution of tin dioxide and antimonous oxide, and the mixture is stirred and mixed uniformly for 2 hours, and then the mixture is stirred to be dry in a water bath kettle at the temperature of 85 ℃. Drying at 120 ℃ overnight, heating to 900 ℃ at a speed of 3 ℃/min in a calciner under the protection of nitrogen, preserving heat for 2 hours, soaking and vibrating overnight with hydrochloric acid with a mass concentration of 5% after calcination, removing impurities, finally washing with deionized water until washing water is neutral, and drying at 120 ℃ for 2 hours to obtain the tin-antimony mesoporous carbon catalyst.
The mesoporous carbon is prepared by the following steps:
s1: 10g of sheared waste straw and 200mL of dilute sulfuric acid are put into a reaction kettle to react for 12 hours at 150 ℃, suction filtration is carried out, 30mL of 0.5M NaOH solution is added for activation, stirring is carried out at 85 ℃ until the mixture is dry, and the mixture is dried at 120 ℃ overnight, thus obtaining the mesoporous carbon precursor.
S2: heating to 600 ℃ at a speed of 2 ℃/min under the protection of nitrogen in a calciner, preserving heat for 3 hours, calcining and carbonizing, soaking and oscillating with 200mL 10wt% hydrofluoric acid overnight after calcining, removing impurities, washing with deionized water until washing water is neutral, and drying at 120 ℃ for 2 hours to obtain mesoporous carbon.
The tin-antimony mesoporous carbon catalyst (20 Sn-25 Sb/BC) prepared in this example has a tin loading of 20%, an antimony loading of 25%, and a specific chartArea 1010m 2 /g, pore size 7.4nm.
In another aspect, the present embodiment provides an application of the catalyst for preparing 2-cyanopyridine by catalytic ammoxidation, which is applied to preparing 2-cyanopyridine by catalytic ammoxidation of 2-picoline, and specifically comprises the following steps: 1000mL of the tin-antimony mesoporous carbon catalyst (20 Sn-25 Sb/BC) of the embodiment is filled in a tubular fixed bed micro-reactor, the temperature of the reactor filled with the catalyst is raised to 350 ℃, industrial 2-methylpyridine and ammonia water are used as raw materials, air and ammonia gas are introduced for reaction, and the preheating temperature of the 2-methylpyridine, the ammonia water, oxygen and ammonia gas before entering the reactor is controlled to be 230 ℃; the molar ratio of the air, the 2-methylpyridine, the ammonia gas and the ammonia water is 245:1.1:54:1, the reaction time is about 2 seconds, the reaction gas is obtained, the reaction gas is condensed, the condensate is layered by a layering kettle, the residence time of the lower layer of the 2-cyanopyridine in the layering kettle is controlled to be 30 minutes, the lower layer of the 2-cyanopyridine is continuously pumped into a rectifying kettle, and the 2-cyanopyridine is rectified at the kettle temperature of 140 ℃ to obtain a 2-cyanopyridine finished product. The conversion of the raw materials and the yield of the product were measured by liquid chromatography. In this example, the conversion of 2-methylpyridine was 99.9%, and the yield of 2-cyanopyridine was 88.6%.
Example 2
This example provides a catalyst for catalyzing ammoxidation to prepare 2-cyanopyridine and its application, the specific embodiment is the same as in example 1 except that: a mixed solution of tin dioxide and antimony trioxide was prepared from 200ml of deionized water, 10.4g of tin dioxide and 5g of antimony trioxide.
The tin-antimony mesoporous carbon catalyst (25 Sn-25 Sb/BC) prepared in the embodiment has a tin loading of 25%, an antimony loading of 25% and a specific surface area of 1021m 2 And/g, pore diameter 6.8nm.
In this example, the conversion of 2-methylpyridine was 99.9%, and the yield of 2-cyanopyridine was 89.2%.
Example 3
This example provides a catalyst for catalyzing ammoxidation to prepare 2-cyanopyridine and its application, the specific embodiment is the same as in example 1 except that: a mixed solution of tin dioxide and antimony trioxide was prepared from 200ml of deionized water, 8.4g of tin dioxide and 8g of antimony trioxide.
The tin-antimony mesoporous carbon catalyst (20 Sn-30 Sb/BC) prepared in the embodiment has a tin loading of 20%, an antimony loading of 30% and a specific surface area of 1015m 2 And/g, pore diameter 6.5nm.
In this example, the conversion of 2-methylpyridine was 99.9%, and the yield of 2-cyanopyridine was 89.4%.
Example 4
This example provides a catalyst for catalyzing ammoxidation to prepare 2-cyanopyridine and its application, the specific embodiment is the same as in example 1 except that: a mixed solution of tin dioxide and antimony trioxide was prepared from 200ml of deionized water, 10.4g of tin dioxide and 8g of antimony trioxide.
The tin loading amount in the tin-antimony mesoporous carbon catalyst (25 Sn-30 Sb/BC) prepared in the embodiment is 25%, the antimony loading amount is 30%, and the specific surface area is 1108m 2 And/g, pore size 5.9nm.
In this example, the conversion of 2-methylpyridine was 99.9%, and the yield of 2-cyanopyridine was 90.8%.
Example 5
This example provides a catalyst for catalyzing ammoxidation to prepare 2-cyanopyridine and its application, the specific embodiment is the same as in example 1 except that: a mixed solution of tin dioxide and antimony trioxide was prepared from 200ml of deionized water, 12.5g of tin dioxide and 9.4g of antimony trioxide.
The tin loading amount in the tin-antimony mesoporous carbon catalyst (30 Sn-35 Sb/BC) prepared in the embodiment is 30%, the antimony loading amount is 35%, and the specific surface area is 997m 2 And/g, pore size 7.8nm.
In this example, the conversion of 2-methylpyridine was 99.9%, and the yield of 2-cyanopyridine was 86.7%.
Claims (10)
1. The catalyst for preparing 2-cyanopyridine by catalytic ammoxidation is characterized by being a tin-antimony mesoporous carbon catalyst and prepared by the following method:
mesoporous carbon is added into a mixed solution of tin dioxide and antimonous oxide, and after stirring and mixing uniformly, the mesoporous carbon catalyst is obtained after drying, calcining, acid leaching treatment, water washing, filtering and drying.
2. The catalyst for catalytic ammoxidation of claim 1, wherein the concentration of tin dioxide in the mixed solution of tin dioxide and antimony trioxide is 0.04-0.07 g/mL and the concentration of antimony trioxide is 0.02-0.05 g/mL.
3. The catalyst for catalytic ammoxidation of claim 1, wherein the calcination is performed at a temperature rise program of 2-5 ℃/min to 800-1000 ℃ and then for 2-5 hours.
4. The catalyst for preparing 2-cyanopyridine by catalytic ammoxidation of claim 1, wherein the mass fraction of tin element in the catalyst is 20-30% and the mass fraction of antimony element is 25-35%.
5. The catalyst for catalyzing ammoxidation to prepare 2-cyanopyridine of claim 1, wherein the specific surface area of the catalyst is 850-1200 m 2 /g。
6. The catalyst for catalyzing ammoxidation to prepare 2-cyanopyridine of claim 1, wherein the pore size of the catalyst is 5.5-10.8 nm.
7. The catalyst for catalytic ammoxidation of any one of claims 1 to 4, wherein the mesoporous carbon is prepared by:
s1: mixing straw with inorganic acid for reaction, filtering, adding alkali solution for activation, and drying to obtain mesoporous carbon precursor;
s2: calcining the mesoporous carbon precursor under the protection of inert gas, soaking the calcined mesoporous carbon precursor in strong acid, removing impurities, washing with water, and drying to obtain the mesoporous carbon.
8. The catalyst for catalytic ammoxidation of claim 5, wherein the calcination in step S2 is performed at a temperature elevation program of 500-700 ℃ at a rate of 1-3 ℃/min, followed by heat preservation for 2-5 hours.
9. Use of a catalyst according to any one of claims 1 to 8 for catalyzing ammoxidation to produce 2-cyanopyridine.
10. The use of a catalyst for catalyzing an ammoxidation reaction to produce 2-cyanopyridine of claim 9, wherein the 2-picoline ammoxidation step comprises: filling the catalyst according to any one of claims 1-8 in a tubular fixed bed reactor, adding 2-methylpyridine and ammonia water, introducing oxygen-containing gas and ammonia gas, reacting to obtain reaction gas, condensing the reaction gas, layering, and rectifying to obtain the finished product 2-cyanopyridine.
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