CN115228463B - Composite catalyst and nicotinic acid production method - Google Patents
Composite catalyst and nicotinic acid production method Download PDFInfo
- Publication number
- CN115228463B CN115228463B CN202210906523.7A CN202210906523A CN115228463B CN 115228463 B CN115228463 B CN 115228463B CN 202210906523 A CN202210906523 A CN 202210906523A CN 115228463 B CN115228463 B CN 115228463B
- Authority
- CN
- China
- Prior art keywords
- nicotinic acid
- composite catalyst
- cellulose ether
- vanadium pentoxide
- titanium dioxide
- 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.)
- Active
Links
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 229960003512 nicotinic acid Drugs 0.000 title claims abstract description 72
- 235000001968 nicotinic acid Nutrition 0.000 title claims abstract description 72
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract description 3
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 19
- 235000010215 titanium dioxide Nutrition 0.000 claims description 19
- 239000012043 crude product Substances 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229920000447 polyanionic polymer Polymers 0.000 claims description 3
- 239000001038 titanium pigment Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 229920006321 anionic cellulose Polymers 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000019160 vitamin B3 Nutrition 0.000 description 2
- 239000011708 vitamin B3 Substances 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 206010063409 Acarodermatitis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 229930003537 Vitamin B3 Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 208000005687 scabies Diseases 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
Classifications
-
- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
-
- 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
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- 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
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
- C07D213/807—Processes of preparation by oxidation of pyridines or condensed pyridines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite catalyst and a nicotinic acid production method, and belongs to the field of fine chemical engineering. The invention takes titanium dioxide as a carrier, vanadium pentoxide as an active matrix and cellulose ether as an adhesive, and the titanium dioxide, the vanadium pentoxide and a cellulose ether aqueous solution with certain viscosity are uniformly mixed, and then the composite catalyst is obtained through spray drying or vacuum drying. When the catalyst is used for nicotinic acid production, the nicotinic acid yield is high, the reaction condition is mild, the cost is low, and the catalyst has good popularization and application values.
Description
Technical Field
The invention relates to the field of fine chemical engineering, and particularly provides a composite catalyst and a nicotinic acid production method.
Background
Nicotinic acid, chinese alias: pyridine-3-carboxylic acid; nicotinic acid; anti-scabies factor, vitamin PP, also known as vitamin B3, CAS number: 59-67-6. It is one of 13 vitamins necessary for human body, is a water-soluble vitamin, belongs to vitamin B group, and is a vitamin with simplest structure and most stable physicochemical property. English: nicotinic acid has little niacin toxicity. Natural nicotinic acid is present in animals and plants, has extremely low content, and is almost impossible to extract from the nicotinic acid, but the nicotinic acid is a fine chemical product which has very wide application, and is widely applied to the medicine and feed industry and also applied to the auxiliary agent of dye and daily chemical industry.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the composite catalyst with simple process and high production efficiency.
The invention further aims to provide a production method of nicotinic acid.
The technical scheme adopted for solving the technical problems is as follows: the composite catalyst is characterized in that titanium white powder is used as a carrier, vanadium pentoxide is used as an active matrix, cellulose ether is used as an adhesive, and the titanium white powder, the vanadium pentoxide and a cellulose ether aqueous solution with certain viscosity are uniformly mixed and then subjected to spray drying or vacuum drying to obtain the composite catalyst.
Preferably, the preparation method of the composite catalyst comprises the following steps:
s1, uniformly mixing titanium dioxide and a cellulose ether aqueous solution with certain viscosity;
s2, adding vanadium pentoxide and uniformly mixing;
s3, spray drying or vacuum drying to obtain the composite catalyst.
Preferably, the mass ratio of the cellulose ether aqueous solution to the vanadium pentoxide to the titanium dioxide is 1:0.1-0.9:0.1 to 0.9, preferably 1:0.2 to 0.6:0.2 to 0.8, particularly preferably 1:0.3 to 0.5:0.3-0.6. The aqueous solution of the cellulose ether has a viscosity of 10 to 500cps, preferably 50 to 350cps, and particularly preferably 100 to 250cps. The cellulose ether may be any cellulose ether substance which is still tacky at high temperatures (above 150 ℃) and can release carbon dioxide, and may be a water-soluble nonionic cellulose ether, an anionic cellulose ether, a cationic cellulose ether or an amphoteric ion cellulose ether, preferably an anionic pirn ether, particularly preferably a polyanion cellulose ether PAC.
Preferably, the titanium dioxide is rutile titanium dioxide with better thermal stability.
Preferably, in the step S1 and the step S2, the materials are mixed by unidirectional stirring. The unidirectional stirring may be clockwise stirring or counterclockwise stirring.
Step S1 can be to dissolve cellulose ether to a certain viscosity, then add titanium pigment, and stir clockwise or anticlockwise until uniform.
Step S2 may be to add vanadium pentoxide into the reaction system slowly and batchwise, and then uniformly stir in the stirring direction of step S1.
Preferably, in the step S3, spray drying is adopted, the temperature at the inlet is 120-220 ℃, the temperature at the outlet is below 100 ℃, and the drying gas is air or inert gas.
Preferably, in step S2, vanadium pentoxide is added together with an appropriate amount of an acidic oxide, which may be Mn 2 O 7 、SiO 2 Or P 2 O 5 Mn is particularly preferred 2 O 7 Or SiO 2 To further increase the yield of nicotinic acid.
Preferably, the mass ratio of the acid oxide to the titanium dioxide is 0.01-0.1:1, preferably 0.02-0.08:1, particularly preferably from 0.03 to 0.05:1.
the production process of nicotinic acid features that air (including oxygen-enriched air) or oxygen is used as oxidant and gaseous 3-methyl pyridine is oxidized under the action of the composite catalyst to obtain crude nicotinic acid product.
Preferably, the nicotinic acid crude product is absorbed by hot ethanol at 70-80 ℃ and then is cooled and crystallized to obtain the high-purity nicotinic acid product.
Preferably, the mass ratio of the oxidant (air), the 3-methylpyridine and the composite catalyst is 1:0.1-0.9:0.1 to 0.9, preferably 1:0.2 to 0.6:0.2 to 0.8, particularly preferably 1:0.3 to 0.5:0.3-0.7; the reaction temperature is 120 to 480 ℃, preferably 180 to 350 ℃, particularly preferably 200 to 300 ℃.
The nicotinic acid production method of the invention can be carried out in a conventional fixed bed reactor, a fluidized bed reactor or a high-pressure reaction kettle.
Compared with the prior art, the composite catalyst and the nicotinic acid production method have the following outstanding beneficial effects:
and firstly, using cellulose ether as a binder, and coating the vanadium pentoxide and the titanium pigment by high-efficiency combination, so that the stable and high-efficiency composite catalyst can be obtained through a conventional spraying or drying process.
The PAC cellulose ether is resistant to a certain high temperature, is low in cost and is easy to obtain, and the preparation cost of the composite catalyst can be further reduced.
(III) when the composite catalyst is used for preparing nicotinic acid, the binder cellulose ether can generate a small amount of CO at high temperature 2 As an acidic oxide, the yield of nicotinic acid can be further improved as measured by an infrared gas analyzer.
And fourthly, when the composite catalyst is used for preparing the nicotinic acid, the operation is simple, the reaction condition is mild, the yield of the nicotinic acid is high, the cost is low, and the industrial production is facilitated.
Detailed Description
The invention will now be further illustrated with reference to specific examples, which are not intended to limit the scope of the invention.
The parts by weight of the raw materials in the following examples are mass ratios (m/m) unless otherwise specified.
Example 1:
[ preparation of composite catalyst ]
S1, preparing PAC aqueous solution with the viscosity of 10cps from poly-anionic cellulose ether PAC, adding 0.1 part of carrier rutile type titanium dioxide into 1 part of PAC aqueous solution, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.1 part of vanadium pentoxide powder and 0.001 part of acidic oxide Mn in batches 2 O 7 Uniformly stirring in the clockwise direction to prevent bubbles from occurring and poor coating effect from occurring;
s3, spray drying to prepare the composite catalyst, wherein the temperature of inlet drying gas is 120 ℃.
[ nicotinic acid production Process ]
And (3) putting 0.1 part of the composite catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.1 part of gas phase 3-methylpyridine under the action of the composite catalyst at 120 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield was 47% (mass yield based on 3-picoline).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 320ppm by sampling three times.
Comparative example 1:
[ preparation of conventional catalysts ]
S1, adding 0.1 part of carrier rutile type titanium dioxide into 1 part of deionized water, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.1 part of vanadium pentoxide powder and 0.001 part of acidic oxide Mn in batches 2 O 7 Uniformly stirring in the clockwise direction to prevent bubbles;
s3, spray drying to prepare the composite catalyst, wherein the temperature of inlet drying gas is 120 ℃.
[ nicotinic acid production Process ]
And (3) placing 0.1 part of conventional catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.1 part of gas phase 3-methylpyridine under the action of the conventional catalyst at 120 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 38% (the mass yield is converted by taking 3-picoline as a main component).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 310ppm by sampling three times.
Example 2:
[ preparation of composite catalyst ]
S1, preparing PAC aqueous solution with the viscosity of 500cps from poly-anionic cellulose ether PAC, adding 0.9 part of carrier rutile type titanium dioxide into 1 part of PAC aqueous solution, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.9 part of vanadium pentoxide powder and 0.09 part of acidic oxide Mn in batches 2 O 7 Uniformly stirring in the clockwise direction to prevent bubbles from occurring and poor coating effect from occurring;
s3, spray drying to prepare the composite catalyst, wherein the inlet drying gas temperature is 220 ℃.
[ nicotinic acid production Process ]
And (3) putting 0.9 part of the composite catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.9 part of gas phase 3-methylpyridine under the action of the composite catalyst at 480 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 41 percent (the mass yield is converted by taking 3-picoline as a main component).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 370ppm by sampling three times.
Example 3:
[ preparation of composite catalyst ]
S1, preparing PAC aqueous solution with the viscosity of 300cps from poly-anionic cellulose ether PAC, adding 0.5 part of carrier rutile type titanium dioxide into 1 part of PAC aqueous solution, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.7 part of vanadium pentoxide powder and 0.04 part of acidic oxide SiO in batches 2 Uniformly stirring in the clockwise direction to prevent bubbles from occurring and poor coating effect from occurring;
s3, spray drying to prepare the composite catalyst, wherein the temperature of inlet drying gas is 160 ℃.
[ nicotinic acid production Process ]
And (3) putting 0.8 part of the composite catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.3 part of gas phase 3-methylpyridine under the action of the composite catalyst at 360 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield was 62% (mass yield based on 3-picoline).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 345ppm by sampling three times.
Example 4:
[ preparation of composite catalyst ]
S1, preparing PAC aqueous solution with viscosity of 200cps from poly-anionic cellulose ether PAC, adding 0.4 part of carrier rutile type titanium dioxide into 1 part of PAC aqueous solution, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.5 part of vanadium pentoxide powder and 0.02 part of acidic oxide Mn in batches 2 O 7 Uniformly stirring in the clockwise direction to prevent bubbles from occurring and poor coating effect from occurring;
s3, spray drying to prepare the composite catalyst, wherein the temperature of inlet drying gas is 160 ℃.
[ nicotinic acid production Process ]
And (3) putting 0.5 part of the composite catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.4 part of gas phase 3-methylpyridine under the action of the composite catalyst at 260 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 81 percent (the mass yield is converted by taking 3-picoline as a main component).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value of the three samples was about 335ppm.
Comparative example 4:
[ preparation of conventional catalysts ]
S1, adding 0.4 part of carrier rutile type titanium dioxide into 1 part of deionized water, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.5 part of vanadium pentoxide powder and 0.02 part of acidic oxide Mn in batches 2 O 7 Stirring uniformly in the clockwise direction;
s3, preparing a conventional catalyst by spray drying, wherein the temperature of inlet drying gas is 160 ℃.
[ nicotinic acid production Process ]
And (3) placing 0.5 part of conventional catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.4 part of gas-phase 3-methylpyridine under the action of the conventional catalyst at 260 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 72 percent (the mass yield is converted by taking 3-picoline as a main component).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 315ppm by sampling three times.
Example 5:
[ nicotinic acid production Process ]
0.5 part of composite catalyst (same as in example 4) is placed in a fixed bed reactor, 0.3 part of oxygen is used as an oxidant, and 0.4 part of gas phase 3-methylpyridine is oxidized under the action of the composite catalyst at 260 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 82 percent (the mass yield is converted by taking 3-picoline as a main component).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 25ppm by sampling three times.
Example 6:
[ preparation of composite catalyst ]
S1, preparing PAC aqueous solution with viscosity of 200cps from poly-anionic cellulose ether PAC, adding 0.4 part of carrier rutile type titanium dioxide into 1 part of PAC aqueous solution, and uniformly stirring in a clockwise direction;
s2, slowly adding 0.5 part of vanadium pentoxide powder and 0.04 part of acidic oxide SiO in batches 2 Uniformly stirring in the clockwise direction to prevent bubbles from occurring and poor coating effect from occurring;
s3, spray drying to prepare the composite catalyst, wherein the temperature of inlet drying gas is 160 ℃.
[ nicotinic acid production Process ]
And (3) putting 0.5 part of the composite catalyst into a fixed bed reactor, taking 1 part of air as an oxidant, and oxidizing 0.4 part of gas phase 3-methylpyridine under the action of the composite catalyst at 260 ℃ to obtain a nicotinic acid crude product. And (3) absorbing the nicotinic acid crude product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 79 percent (the mass yield is converted by taking 3-picoline as a main component).
The carbon dioxide content of the tail gas was measured by an infrared gas analyzer, and the average value was about 340ppm by sampling three times.
As can be seen from the experimental data of example 4, comparative example 4 and example 5, under the same experimental conditions, a small amount of carbon dioxide (about 20 ppm) released from the composite catalyst resulted in an improved yield of the target product.
The above embodiments are only preferred embodiments of the present invention, and it is intended that the common variations and substitutions made by those skilled in the art within the scope of the technical solution of the present invention are included in the scope of the present invention.
Claims (6)
1. The production method of nicotinic acid is characterized in that air or oxygen is used as oxidant, gas phase 3-methylpyridine is oxidized under the action of composite catalyst to obtain crude product of nicotinic acid,
the composite catalyst takes titanium dioxide as a carrier, vanadium pentoxide as an active matrix and polyanion cellulose ether PAC as an adhesive, the titanium dioxide, the vanadium pentoxide and polyanion cellulose ether PAC aqueous solution with certain viscosity are uniformly mixed, and then spray drying or vacuum drying is carried out to obtain the composite catalyst,
the mass ratio of the polyanionic cellulose ether PAC aqueous solution to the vanadium pentoxide to the titanium dioxide is 1:0.2-0.6:0.2 to 0.8, the viscosity of the aqueous solution of cellulose ether is 100 to 250cps,
the preparation method of the composite catalyst comprises the following steps:
s1, uniformly mixing titanium dioxide with a polyanionic cellulose ether PAC aqueous solution with certain viscosity;
s2, adding vanadium pentoxide and a proper amount of acidic oxide, and uniformly mixing, wherein the acidic oxide is Mn 2 O 7 Or SiO 2 ；
S3, spray drying or vacuum drying to obtain the composite catalyst.
2. The method for producing nicotinic acid according to claim 1, wherein the titanium white powder is rutile titanium white powder.
3. The method for producing nicotinic acid according to claim 1 or 2, wherein the materials in step S1 and step S2 are mixed by unidirectional stirring.
4. The method according to claim 1 or 2, wherein in step S3, spray drying is performed, the temperature at the inlet is 120-220 ℃, the temperature at the outlet is 100 ℃ or less, and the drying gas is air or inert gas.
5. The method for producing nicotinic acid according to claim 1 or 2, wherein the mass ratio of the acidic oxide to the titanium pigment is 0.01-0.1:1.
6. a process for producing nicotinic acid according to claim 1 or 2, wherein,
the mass ratio of the oxidant to the 3-methylpyridine to the composite catalyst is 1:0.1-0.9:0.1-0.9, and the reaction temperature is 120-480 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210906523.7A CN115228463B (en) | 2022-07-29 | 2022-07-29 | Composite catalyst and nicotinic acid production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210906523.7A CN115228463B (en) | 2022-07-29 | 2022-07-29 | Composite catalyst and nicotinic acid production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115228463A CN115228463A (en) | 2022-10-25 |
| CN115228463B true CN115228463B (en) | 2024-01-26 |
Family
ID=83677396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210906523.7A Active CN115228463B (en) | 2022-07-29 | 2022-07-29 | Composite catalyst and nicotinic acid production method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115228463B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247190A (en) * | 1998-09-01 | 2000-03-15 | 底古萨－胡尔斯股份公司 | Method for preparing nicotinic acid |
| CN104128195A (en) * | 2014-07-04 | 2014-11-05 | 兰州大学 | Catalyst for preparing cyanopyridine and preparation method thereof |
| CN106492791A (en) * | 2016-11-17 | 2017-03-15 | 西南化工研究设计院有限公司 | A kind of middle low-temperature denitration catalyst and preparation method thereof |
| CN108126723A (en) * | 2017-12-29 | 2018-06-08 | 兄弟科技股份有限公司 | A kind of catalyst for being used to prepare nicotinonitrile and preparation method thereof |
| CN108889296A (en) * | 2018-07-31 | 2018-11-27 | 包头稀土研究院 | SCR catalyst slurries and its preparation method and application |
| CN109225203A (en) * | 2018-09-30 | 2019-01-18 | 中自环保科技股份有限公司 | A kind of vanadium base oxide SCR catalyst preparation method and its catalyst of preparation |
| RU2704138C1 (en) * | 2019-07-24 | 2019-10-24 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Nicotinic acid production method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI263637B (en) * | 2004-04-05 | 2006-10-11 | Chang Chun Petrochemical Co | Process for preparing nicotinic acid and catalyst used in the method |
| EP3116648A1 (en) * | 2014-02-21 | 2017-01-18 | Huntsman P&A Germany GmbH | Catalyst precursor material on a tio2 basis, and production and use thereof |
-
2022
- 2022-07-29 CN CN202210906523.7A patent/CN115228463B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247190A (en) * | 1998-09-01 | 2000-03-15 | 底古萨－胡尔斯股份公司 | Method for preparing nicotinic acid |
| CN104128195A (en) * | 2014-07-04 | 2014-11-05 | 兰州大学 | Catalyst for preparing cyanopyridine and preparation method thereof |
| CN106492791A (en) * | 2016-11-17 | 2017-03-15 | 西南化工研究设计院有限公司 | A kind of middle low-temperature denitration catalyst and preparation method thereof |
| CN108126723A (en) * | 2017-12-29 | 2018-06-08 | 兄弟科技股份有限公司 | A kind of catalyst for being used to prepare nicotinonitrile and preparation method thereof |
| CN108889296A (en) * | 2018-07-31 | 2018-11-27 | 包头稀土研究院 | SCR catalyst slurries and its preparation method and application |
| CN109225203A (en) * | 2018-09-30 | 2019-01-18 | 中自环保科技股份有限公司 | A kind of vanadium base oxide SCR catalyst preparation method and its catalyst of preparation |
| RU2704138C1 (en) * | 2019-07-24 | 2019-10-24 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Nicotinic acid production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115228463A (en) | 2022-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8435467B2 (en) | Process for preparing ammonium metatungstate | |
| CN114225848B (en) | Device and method for preparing butene-2-acid through high-yield continuous oxidation | |
| CN115228463B (en) | Composite catalyst and nicotinic acid production method | |
| CN115215824A (en) | Preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride | |
| CN112321459A (en) | Method for synthesizing carbasalate calcium | |
| CN109205673A (en) | The method for preparing vanadium trioxide | |
| US3862960A (en) | Process for the oxidation of orthoxylene or naphthalene to phthalic anhydride | |
| CN116393120B (en) | A method and catalyst for preparing D,L-tartaric acid by microchannel reaction | |
| CN114315711A (en) | Method for producing 3-cyanopyridine by using fluidized bed and catalyst used in method | |
| CN113548995A (en) | Preparation method of alpha-pyrrolidone | |
| CN112812071B (en) | Method for continuously synthesizing 1H-1,2, 3-triazole by using microchannel reactor | |
| CN114835605B (en) | Synthesis method of diphenyl ketone hydrazone | |
| CN115974748A (en) | Process for producing methylpyrrolidone | |
| CN107488111B (en) | Method for synthesizing propyl gallate by solid acid catalysis | |
| CN116162067B (en) | Preparation method of prothioconazole | |
| CN114291856B (en) | A method for preparing a noble metal catalyst based on ectoine | |
| CN115368328B (en) | Preparation method and application of caronic anhydride | |
| CN111097427A (en) | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone | |
| CN112390753B (en) | Dihaloquinolinic acid intermediate and preparation method thereof | |
| CN117229248B (en) | Method for preparing and purifying vitronectin by using solid alkali | |
| SK149696A3 (en) | Catalyst mixture for oxidative ammonolysis of alkylpyridines and method of manufacture thereof | |
| DE478726C (en) | Process for the preparation of maleic acid | |
| CN107497474B (en) | Zeolite catalyst for synthesizing propyl gallate | |
| CN117776904A (en) | Method for preparing calcium gluconate by micro-channel continuous flow reaction technology | |
| CN117417295A (en) | Synthesis method of 5-methylnicotinic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |