CN115228463A - Composite catalyst and nicotinic acid production method - Google Patents
Composite catalyst and nicotinic acid production method Download PDFInfo
- Publication number
- CN115228463A CN115228463A CN202210906523.7A CN202210906523A CN115228463A CN 115228463 A CN115228463 A CN 115228463A CN 202210906523 A CN202210906523 A CN 202210906523A CN 115228463 A CN115228463 A CN 115228463A
- Authority
- CN
- China
- Prior art keywords
- composite catalyst
- nicotinic acid
- cellulose ether
- titanium dioxide
- vanadium pentoxide
- 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
Links
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229960003512 nicotinic acid Drugs 0.000 title claims abstract description 60
- 235000001968 nicotinic acid Nutrition 0.000 title claims abstract description 60
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920003086 cellulose ether Polymers 0.000 claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001694 spray drying Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 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 30
- 238000003756 stirring Methods 0.000 claims description 15
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000034 method Methods 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
- 239000000047 product Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 239000001569 carbon dioxide Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 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
- 206010029400 Nicotinic acid deficiency Diseases 0.000 description 1
- 208000002141 Pellagra Diseases 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 229930003537 Vitamin B3 Natural products 0.000 description 1
- 229920006321 anionic cellulose Polymers 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
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 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
- POXTUDOMVMUXLS-UHFFFAOYSA-N vicarin Natural products COc1c2OCOc2cc3OC(=C(C(=O)c13)c4ccccc4O)O POXTUDOMVMUXLS-UHFFFAOYSA-N 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 production method of nicotinic acid, belonging to the field of fine chemical engineering. The composite catalyst is prepared by uniformly mixing titanium dioxide, vanadium pentoxide and a cellulose ether aqueous solution with certain viscosity by using titanium dioxide as a carrier, vanadium pentoxide as an active matrix and cellulose ether as a binder, and then performing 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 production method of nicotinic acid.
Background
Nicotinic acid, a chinese alias: pyridine-3-carboxylic acid; nicotinic acid; pellagra-resistant factor, vitamin PP, also known as vitamin B3, CAS No.: 59-67-6. It is one of the 13 vitamins essential to human body, is a water-soluble vitamin, belongs to vitamin B group, and is a vitamin with simplest structure and most stable physicochemical properties. English: nicotinic acid, niacin has little toxicity. The natural nicotinic acid is mostly present in animal and plant bodies, has extremely low content, is almost impossible to extract from the animal and plant bodies, is a fine chemical product with wide application, is widely applied to the medicine and feed industries, and is also applied to the dye and the auxiliary agent of the 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 by the invention for solving the technical problems is as follows: the composite catalyst is characterized in that titanium dioxide is used as a carrier, vanadium pentoxide is used as an active matrix, cellulose ether is used as a binder, and the titanium dioxide, the vanadium pentoxide and a cellulose ether aqueous solution with certain viscosity are uniformly mixed and then are 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;
and 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, preferably 1.2-0.6: 0.2 to 0.8, particularly preferably 1.3 to 0.5:0.3-0.6. The viscosity of the aqueous cellulose ether solution is from 10 to 500cps, preferably from 50 to 350cps, particularly preferably from 100 to 250cps. The cellulose ether can be any cellulose ether substance which has viscosity at high temperature (above 150 ℃) and can release carbon dioxide, and can be water-soluble nonionic cellulose ether, anionic cellulose ether, cationic cellulose ether or zwitterionic cellulose ether, preferably anionic vicarin ether, and particularly preferably polyanionic cellulose ether PAC.
Preferably, the titanium dioxide is rutile titanium dioxide with better thermal stability.
Preferably, when the materials are mixed in step S1 and step S2, unidirectional stirring and mixing are adopted. The unidirectional stirring may be clockwise stirring or counterclockwise stirring.
The step S1 can be that the cellulose ether is dissolved to a certain viscosity, then the titanium dioxide is added, and the mixture is stirred to be uniform in the clockwise direction or the anticlockwise direction.
Step S2 can be to slowly add vanadium pentoxide into the reaction system in batches and then stir the vanadium pentoxide uniformly in the stirring direction of the step S1.
Preferably, when spray drying is used in step S3, the temperature at the inlet is 120-220 deg.C, the temperature at the outlet is below 100 deg.C, and the drying gas is air or inert gas.
Preferably, the vanadium pentoxide is added in step S2 simultaneously with an appropriate amount of an acidic oxide, which may be Mn 2 O 7 、SiO 2 Or P 2 O 5 Particularly preferred is Mn 2 O 7 Or SiO 2 To further improve the yield of nicotinic acid.
Preferably, the mass ratio of the acidic oxide to the titanium dioxide is 0.01-0.1:1, preferably 0.02 to 0.08:1, particularly preferably 0.03 to 0.05:1.
the production method of nicotinic acid is characterized by that it uses air (including oxygen-enriched air) or oxygen as oxidant, and the gas-phase 3-methylpyridine is oxidized under the action of said invented composite catalyst to obtain the crude product of nicotinic acid.
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, preferably 1.2-0.6: 0.2 to 0.8, particularly preferably 1.3 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 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 production method of the nicotinic acid have the following outstanding beneficial effects:
and (I) taking cellulose ether as a binder, efficiently combining and coating vanadium pentoxide and titanium dioxide, and obtaining the stable and efficient composite catalyst by a conventional spraying or drying process.
The PAC cellulose ether (II) has certain high temperature resistance, is cheap and easy to obtain, and can further reduce the preparation cost of the composite catalyst.
(III) when the composite catalyst of the invention is used for preparing nicotinic acid, the binder cellulose ether can generate a small amount of CO at high temperature 2 The nicotinic acid yield can be further improved when the acidic oxide is detected 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 present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Unless otherwise specified, the weighed parts of the raw materials in the following examples are given by mass ratio (m/m).
Example 1:
[ PREPARATION OF COMPOSITE CATALYST ]
S1, preparing polyanionic cellulose ether PAC into a PAC aqueous solution with the viscosity of 10cps, then adding 0.1 part of carrier rutile type titanium dioxide into 1 part of the 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 The materials are uniformly stirred in the clockwise direction, so that the phenomena of bubbles and poor coating effect are prevented;
s3, preparing the composite catalyst by spray drying, wherein the temperature of an inlet dry gas is 120 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.1 part of composite catalyst is put into a fixed bed reactor, 1 part of air is taken as an oxidant, and 0.1 part of gas phase 3-methylpyridine is oxidized under the action of the composite catalyst at 120 ℃ to obtain a nicotinic acid crude product. Absorbing the crude nicotinic acid product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 47% (converted by taking 3-methylpyridine as a main mass yield).
The carbon dioxide content of the tail gas is tested by an infrared gas analyzer, and the average value of three sampling times is about 320ppm.
Comparative example 1:
[ PREPARATION OF COMMON CATALYST ]
S1, adding 0.1 part of carrier rutile type titanium dioxide into 1 part of deionized water, and uniformly stirring clockwise;
s2, slowly adding 0.1 part of vanadium pentoxide powder and 0.001 part of acidic oxide Mn in batches 2 O 7 The materials are uniformly stirred in the clockwise direction to prevent bubbles;
s3, preparing the composite catalyst by spray drying, wherein the temperature of an inlet dry gas is 120 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.1 part of conventional catalyst is put into a fixed bed reactor, 1 part of air is taken as an oxidant, and 0.1 part of gas-phase 3-methylpyridine is oxidized under the action of the conventional catalyst and at the temperature of 120 ℃ to obtain a nicotinic acid crude product. Absorbing the crude nicotinic acid product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 38 percent (converted by taking 3-methylpyridine as a main mass yield).
The carbon dioxide content of the tail gas is tested by an infrared gas analyzer, and the average value of three sampling times is about 310ppm.
Example 2:
[ PREPARATION OF COMPOSITE CATALYST ]
S1, preparing polyanionic cellulose ether PAC into a PAC aqueous solution with the viscosity of 500cps, then adding 0.9 part of carrier rutile type titanium dioxide into 1 part of the 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 The materials are uniformly stirred in the clockwise direction, so that the phenomena of bubbles and poor coating effect are prevented;
s3, preparing the composite catalyst by spray drying, wherein the temperature of an inlet dry gas is 220 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.9 part of composite catalyst is put into a fixed bed reactor, 1 part of air is taken as an oxidant, and 0.9 part of gas phase 3-methylpyridine is oxidized under the action of the composite catalyst and at 480 ℃ to obtain a crude nicotinic acid product. Absorbing the crude nicotinic acid product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The yield of nicotinic acid is 41 percent (converted by the main mass yield of 3-picoline).
The carbon dioxide content of the tail gas is tested by an infrared gas analyzer, and the average value of three sampling times is about 370ppm.
Example 3:
[ PREPARATION OF COMPOSITE CATALYST ]
S1, preparing polyanionic cellulose ether PAC into a PAC aqueous solution with the viscosity of 300cps, then adding 0.5 part of carrier rutile type titanium dioxide into 1 part of the 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 The materials are uniformly stirred in the clockwise direction, so that the phenomena of bubbles and poor coating effect are prevented;
s3, preparing the composite catalyst by spray drying, wherein the temperature of an inlet dry gas is 160 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.8 part of composite catalyst is put into a fixed bed reactor, 1 part of air is taken as an oxidant, and 0.3 part of gas phase 3-methylpyridine is oxidized under the action of the composite catalyst and under the condition of 360 ℃ to obtain a nicotinic acid crude product. Absorbing the crude nicotinic acid product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 62% (converted by taking 3-methylpyridine as a main mass yield).
The carbon dioxide content of the tail gas is tested by an infrared gas analyzer, and the average value of three sampling times is about 345ppm.
Example 4:
[ PREPARATION OF COMPOSITE CATALYST ]
S1, preparing polyanionic cellulose ether PAC into a PAC aqueous solution with the viscosity of 200cps, then adding 0.4 part of carrier rutile type titanium dioxide into 1 part of the 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 The materials are uniformly stirred in the clockwise direction, so that the phenomena of bubbles and poor coating effect are prevented;
s3, preparing the composite catalyst by spray drying, wherein the temperature of an inlet dry gas is 160 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.5 part of composite catalyst is put into a fixed bed reactor, 1 part of air is taken as an oxidant, and 0.4 part of gas phase 3-methylpyridine is oxidized under the action of the composite catalyst at the temperature of 260 ℃ to obtain a crude nicotinic acid product. Absorbing the crude nicotinic acid product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The yield of nicotinic acid is 81 percent (converted by taking 3-methylpyridine as a main mass yield).
The tail gas carbon dioxide content was measured using an infrared gas analyzer and sampled three times to average about 335ppm.
Comparative example 4:
[ PREPARATION OF COMMON CATALYST ]
S1, adding 0.4 part of carrier rutile type titanium dioxide into 1 part of deionized water, and uniformly stirring clockwise;
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 same clockwise direction;
s3, preparing a conventional catalyst by spray drying, wherein the temperature of an inlet dry gas is 160 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.5 part of conventional catalyst is put into a fixed bed reactor, 1 part of air is taken as an oxidant, and 0.4 part of gas-phase 3-methylpyridine is oxidized under the action of the conventional catalyst and at the temperature of 260 ℃ to obtain a nicotinic acid crude product. Absorbing the crude nicotinic acid 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 (converted by taking 3-methylpyridine as a main mass yield).
The carbon dioxide content of the tail gas is tested by an infrared gas analyzer, and the average value of three sampling times is about 315ppm.
Example 5:
[ nicotinic acid production Process ]
0.5 part of composite catalyst (same as example 4) is put into 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 and at the temperature of 260 ℃ to obtain a nicotinic acid crude product. Absorbing the crude nicotinic acid product by hot ethanol (95%) at 75 ℃, and cooling and crystallizing to obtain the high-purity nicotinic acid. The nicotinic acid yield is 82% (converted by taking 3-methylpyridine as a main mass yield).
The tail gas carbon dioxide content was measured using an infrared gas analyzer, and the average value was taken for three times at about 25ppm.
Example 6:
[ PREPARATION OF COMPOSITE CATALYST ]
S1, preparing polyanionic cellulose ether PAC into a PAC aqueous solution with the viscosity of 200cps, then adding 0.4 part of carrier rutile type titanium dioxide into 1 part of the 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 The materials are uniformly stirred in the clockwise direction, so that the phenomena of bubbles and poor coating effect are prevented;
s3, spray drying to prepare the composite catalyst, wherein the temperature of an inlet dry gas is 160 ℃.
[ PRODUCTION TECHNOLOGY OF NICOTIC ACID ]
0.5 part of composite catalyst is put into a fixed bed reactor, 1 part of air is used as an oxidant, and 0.4 part of gas-phase 3-methylpyridine is oxidized at 260 ℃ under the action of the composite catalyst to obtain a nicotinic acid crude product. Absorbing the crude nicotinic acid 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 (converted by taking 3-methylpyridine as a main mass yield).
The carbon dioxide content of the tail gas is tested by an infrared gas analyzer, and the average value of three sampling times is about 340ppm.
As can be seen from the experimental data of example 4, comparative example 4 and example 5, under the same experimental conditions, the composite catalyst releases a small amount of carbon dioxide (about 20 ppm), so that the yield of the target product is improved.
The above-described embodiments are merely preferred embodiments of the present invention, and those skilled in the art should be able to make various changes and substitutions within the scope of the present invention.
Claims (10)
1. The composite catalyst is characterized in that titanium dioxide is used as a carrier, vanadium pentoxide is used as an active matrix, cellulose ether is used as a binder, and the titanium dioxide, the vanadium pentoxide and a cellulose ether aqueous solution with certain viscosity are uniformly mixed and then are subjected to spray drying or vacuum drying to obtain the composite catalyst.
2. The composite catalyst according to claim 1, characterized in that its preparation method comprises:
s1, uniformly mixing titanium dioxide and a cellulose ether aqueous solution with certain viscosity;
s2, adding vanadium pentoxide and uniformly mixing;
and S3, spray drying or vacuum drying to obtain the composite catalyst.
3. The composite catalyst according to claim 1 or 2, wherein the mass ratio of the cellulose ether aqueous solution to the vanadium pentoxide and the titanium dioxide is 1:0.1-0.9, the viscosity of the aqueous solution of cellulose ether is 10-500cps, and the cellulose ether is polyanionic cellulose ether PAC.
4. The composite catalyst according to claim 1 or 2, wherein the titanium dioxide is rutile titanium dioxide.
5. The composite catalyst according to claim 1 or 2, wherein the materials are mixed in step S1 and step S2 by unidirectional stirring.
6. The composite catalyst according to claim 1 or 2, wherein when spray drying is adopted in step S3, 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.
7. The composite catalyst according to claim 1 or 2, wherein an appropriate amount of an acidic oxide is added while adding vanadium pentoxide in step S2, wherein the acidic oxide is Mn 2 O 7 、SiO 2 Or P 2 O 5 。
8. The composite catalyst according to claim 1 or 2, wherein the mass ratio of the acidic oxide to the titanium dioxide is 0.01-0.1:1.
9. the method for producing the nicotinic acid is characterized in that air or oxygen is used as an oxidant, gas-phase 3-methylpyridine is oxidized under the action of a composite catalyst to obtain a crude product of the nicotinic acid, and the composite catalyst is the composite catalyst in any one of claims 1 to 8.
10. The method of producing niacin according to claim 9,
the mass ratio of the oxidant, the 3-methylpyridine and the composite catalyst is 1:0.1-0.9, 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 true CN115228463A (en) | 2022-10-25 |
| CN115228463B 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 (9)
| 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 |
| US20050222421A1 (en) * | 2004-04-05 | 2005-10-06 | Chang Chun Petrochemical Co., Ltd. | Process for preparing nicotinic acid and catalyst used in the method |
| CN104128195A (en) * | 2014-07-04 | 2014-11-05 | 兰州大学 | Catalyst for preparing cyanopyridine and preparation method thereof |
| US20170056855A1 (en) * | 2014-02-21 | 2017-03-02 | Huntsman P&A Germany Gmbh | TiO2 based catalyst precursor material, production thereof and use 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 |
-
2022
- 2022-07-29 CN CN202210906523.7A patent/CN115228463B/en active Active
Patent Citations (9)
| 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 |
| US20050222421A1 (en) * | 2004-04-05 | 2005-10-06 | Chang Chun Petrochemical Co., Ltd. | Process for preparing nicotinic acid and catalyst used in the method |
| US20170056855A1 (en) * | 2014-02-21 | 2017-03-02 | Huntsman P&A Germany Gmbh | TiO2 based catalyst precursor material, production thereof and use thereof |
| 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 |
|---|---|
| CN115228463B (en) | 2024-01-26 |
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 | |
| CN111097468A (en) | Alkyl pyridine ammoxidation catalyst and preparation method thereof | |
| CN100457266C (en) | Manufacturing method of faujasite coated phosphorus heteropoly tungstic acid catalyzer | |
| CN115228463B (en) | Composite catalyst and nicotinic acid production method | |
| CN107572588B (en) | A kind of environment-friendly type sodium tungstate preparation process and its application | |
| CN116393120B (en) | Method and catalyst for preparing D, L-tartaric acid through microchannel reaction | |
| CN107930687A (en) | The method of modifying of TS 1 and its application in solvent-free catalysis lactate prepares pyruvate | |
| CN110437231B (en) | Preparation method of valaciclovir hydrochloride anhydrous crystal form I | |
| CN107262105A (en) | A kind of catalyst of methanol production formaldehyde and preparation method thereof | |
| CN114315711A (en) | Method for producing 3-cyanopyridine by using fluidized bed and catalyst used in method | |
| CN113548995A (en) | Preparation method of alpha-pyrrolidone | |
| DE1518630A1 (en) | Process for the production of oxidized starch | |
| CN107488111B (en) | Method for synthesizing propyl gallate by solid acid catalysis | |
| CN106928135A (en) | A kind of continuous preparation method of N- pyridine-N-oxides | |
| CN111499497A (en) | Preparation method of thymol | |
| CN111097427A (en) | Catalyst for preparing gamma-butyrolactone through maleic anhydride liquid-phase hydrogenation, preparation method and application thereof, and method for preparing gamma-butyrolactone | |
| CN117229248B (en) | Method for preparing and purifying vitronectin by using solid alkali | |
| CN114291856B (en) | Preparation method of precious metal catalyst based on ectoine | |
| CN112390753B (en) | Dihaloquinolinic acid intermediate and preparation method thereof | |
| CN116162067B (en) | Preparation method of prothioconazole | |
| CN116042733B (en) | Synthesis method of glyoxylate or glycine | |
| CN114275807B (en) | Preparation method of indium nitrate solution, preparation method and application of high-activity indium oxide | |
| CN114591170B (en) | Method for preparing glyoxylate by oxidizing glycolate | |
| CN107497474B (en) | Zeolite catalyst for synthesizing propyl gallate |
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 |