CN105498817A - Catalyst for production of trimellitic anhydride and preparation method and application of catalyst - Google Patents
Catalyst for production of trimellitic anhydride and preparation method and application of catalyst Download PDFInfo
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- CN105498817A CN105498817A CN201511013473.6A CN201511013473A CN105498817A CN 105498817 A CN105498817 A CN 105498817A CN 201511013473 A CN201511013473 A CN 201511013473A CN 105498817 A CN105498817 A CN 105498817A
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- China
- Prior art keywords
- catalyst
- trimellitic anhydride
- heteropoly acid
- pseudocumene
- metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 73
- 230000003647 oxidation Effects 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 26
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 38
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 150000004706 metal oxides Chemical class 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 230000018044 dehydration Effects 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000004088 simulation Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 33
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000010936 titanium Substances 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 230000003100 immobilizing effect Effects 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 229910020632 Co Mn Inorganic materials 0.000 description 1
- 229910020678 Co—Mn Inorganic materials 0.000 description 1
- 229910018669 Mn—Co Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
-
- 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
- B01J21/18—Carbon
-
- 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
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- Catalysts (AREA)
Abstract
The invention provides a catalyst for production of trimellitic anhydride and a preparation method of the catalyst and application of the catalyst, belonging to the technical field of chemical industry production. The preparation method comprises the following steps of performing hydrothermal reaction on heteropoly acid and metallic oxide containing vanadium, titanium, manganese and cobalt, and dispersing and immobilizing the heteropoly acid on metallic oxide nanoparticle surface so as to form a metal-heteropoly acid compound; loading metal-heteropoly acid on carbon nanotube surface, performing extrusion forming treatment, and roasting so as to obtain a metal-heteropoly acid loaded carbon nanotube catalyst. The catalyst can be used for pseudocumene gas-phase continuous oxidation synthesis of the trimellitic anhydride, so that the conversion rate in the pseudocumene gas-phase oxidation process can be improved, and the selectivity of the trimellitic anhydride is improved. The catalyst provided by the invention is used for the production of the trimellitic anhydride, and has the advantages of long service life of the catalyst, small use amount of the catalyst, small corrosion to equipment, little equipment investment, high safety factor and low energy consumption.
Description
Technical field
The present invention relates to the Catalysts and its preparation method and purposes that use when a kind of continuous vapour phase oxidation process produces trimellitic anhydride.Belong to chemical technology field.
Background technology
Trimellitic anhydride (TMA) is the important industrial chemicals of organic synthesis industry, can produce the chemicals of multiple unique properties, as plasticizer trioctyl trimellitate (TOTM) (TOTM), and the resin such as polyimides, polyester-imide, water soluble paint and powdery paints etc.The Heavy Aromatic Hydrocarbons of China enriches, utilize wherein main component---pseudocumene (TMB) produces trimellitic anhydride, not only can make full use of Heavy Aromatic Hydrocarbons, can also promote the development of China's chemical industry.
Method mainly continuity method (or batch process) the liquid phase air oxidation technique of current industrial production trimellitic anhydride.Liquid-phase air oxidation is raw material with pseudocumene, makes solvent with acetic acid, is catalyst with the soluble-salt of Co-Mn and bromide, 200 DEG C, carry out oxidation with air under 2.0 ~ 2.3MPa condition and make trimellitic acid, then dehydration generates trimellitic anhydride.Publication number is CN1401642A, the patent of invention that name is called " a kind of method of continuity method liquid phase air oxidation explained hereafter trimellitic anhydride ", describes and have employed continuity method oxidizing process production trimellitic anhydride, obtain higher product yield.CN1915960A with CN1931850A individually discloses the method utilizing intermediate bubble oxidization column multitower series connection continuous oxidation production trimellitic acid and trimellitic acid to become acid anhydride refined raw production of high purity trimellitic anhydride continuously.These all belong to continuity method liquid phase air oxidation technology category.CN101402624A also discloses a kind of method that pseudocumene liquid phase segmenting hydrocarbonylation produces trimellitic anhydride.On batch oxidation device, add catalyst by segmentation, solve the self-inhibiting effect existed in oxidation reaction.
Pseudocumene vapour phase oxidation process is the gaseous oxidation technique with the catalysis of V-Ti system that Nippon Shokubai Kagaku Kogyo Co., Ltd develops in 20 century 70s.But vapour phase oxidation process has no industrialization report.CN1439636A has invented a kind of method of Fixed Bed Gas Phase oxidation pseudocumene trimellitic anhydride.Specifically disclose the mixing of pseudocumene, water vapour and air to send into the tubular reactor that V-Ti system fixed bde catalyst is housed and obtain trimellitic anhydride.The method describes reaction condition in detail, the component of catalyst and preparation, but the trimellitic anhydride low conversion rate obtained, and also the purity of trimellitic anhydride, the selective of catalyst all had much room for improvement with the life-span.
The weak point of above-mentioned two kinds of production methods is as follows respectively:
Liquid-phase air oxidation: the acetic aid medium 1) used has severe corrosive, and operating pressure is high, production equipment need be processed with titanium material, and equipment investment is large; 2) acetic acid consumption amount is large, and recovery process is complicated.3) constantly need add catalyst, consumption is large.
Vapour phase oxidation process: 1) TMB conversion rate of oxidation is low; 2) catalyst choice is not high, and 3) catalyst easy in inactivation, the life-span is short.
Summary of the invention
The object of this invention is to provide a kind of catalyst produced for trimellitic anhydride, continuous vapour phase oxidation process can be used for and produce trimellitic anhydride, and its conversion ratio is high, autophage is few, for the large-scale industrial production of trimellitic anhydride provides technical support.
For this reason, the invention provides following technical scheme: a kind of catalyst produced for trimellitic anhydride, its raw material comprises following components by weight percent:
Heteropoly acid 1 part
Metal oxide 0.1 ~ 0.3 part
CNT 0.45 ~ 0.55 part
Described metal oxide is nano level V
2o
5, TiO
2, MnO and CoO mixture, particle diameter 40 ~ 70nm, wherein V
2o
5with TiO
2between mol ratio be 1:(0.95 ~ 1.05), the mol ratio between MnO and CoO is 1:(0.95 ~ 1.05), [V-
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:(1 ~ 3).
Described heteropoly acid is preferably Dawson structure heteropoly acid.Described CNT is SWCN.
The present invention also provides the preparation method of material a kind of above-mentioned metal-heteropoly acid compound load carbon nano-tube catalyst, comprises the steps:
1) by hydro-thermal reaction, heteropoly acid is disperseed immobilized to metal oxide particle surface, thus form metal-heteropoly acid compound;
2) make metal-heteropoly acid compound load to carbon nano tube surface by the hydroxyl of single tube-surface, extruded, then roasting obtains metal-heteropoly acid compound load carbon nano-tube catalyst.
Time extruded, forming shape is cylindrical, spherical, annular, cloverleaf pattern, tooth are spherical, honeycombed or bird-nest-shaped.Be preferably tooth spherical.
Hydrothermal temperature is 100 ~ 300 DEG C, and the reaction time is 3 ~ 12h; Sintering temperature is 150 ~ 350 DEG C, and roasting time is 5 ~ 15h.
Present invention also offers the purposes that above-mentioned continuous vapour phase oxidation process produces the catalyst of trimellitic anhydride, this catalyst is used for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.
Trimellitic anhydride can be synthesized as follows:
1) metal obtained after roasting-heteropoly acid compound load carbon nano-tube catalyst is fixed on oxidation reaction tower catalyst fixed bed on, multi-layer catalyst layer is set on catalyst fixed bed;
2) raw material pseudocumene first obtains gaseous state pseudocumene by flash of steam device;
3) gaseous state pseudocumene and oxygen-containing gas mixing are passed into oxidation reaction tower; Control at 5 ~ 10h in the mass space velocity of pseudocumene
-1, temperature is at 150 ~ 220 DEG C, and pressure is at 1.0 ~ 2.0MPa; In mixed gas, oxygen quality content is 10 ~ 20%; Described mass space velocity=material quality flow (unit: kgh
-1)/catalyst quality (unit: kg);
4) in oxidation reaction tower, mist is step by step through each layer catalyst layer, and part gaseous state pseudocumene oxidation reaction also dehydration generates vaporific trimellitic anhydride;
5) mixture containing gaseous state pseudocumene and vaporific trimellitic anhydride passes in solid phase trap continuously, carries out trapping and obtain trimellitic anhydride finished product at 140 ~ 160 DEG C.
The voidage of the catalyst layer in oxidation reaction tower successively increases from top to bottom along the direction of described simulation model for mixing gases flows.Described oxygen-containing gas can be air or oxygen.
Continuous vapour phase oxidation process of the present invention produces the catalyst of trimellitic anhydride, heteropoly acid provides acid site, heteropoly acid is the class multinuclear complex acid consisted of oxygen atom ligand bridging different hetero atoms and polyatom, is the Bronsted acid of even intensity, and has redox ability.By changing molecular composition, adjustable acid strength and redox property.CNT is as the carrier of metal-heteropoly acid compound.Containing the active component that vanadium, titanium, manganese, cobalt/cobalt oxide are catalyst, and there is catalyzing cooperation effect.As activated centre vanadium, titanium, manganese, cobalt/cobalt oxide, the oxidation state of these metals is multivalent state, can change mutually between lower valency and high-valence state.That improves in pseudocumene gas phase oxidation process is selective, thus improves the yield of trimellitic anhydride.Pseudocumene gas phase oxidation is the combined process of liquid phase oxidation and dehydration, in other words, in gas phase oxidation process, because of the water direct gasification of course of reaction, and makes the very fast dehydration of trimellitic acid become acid anhydride.The present invention compensate for the weak point of liquid and gas oxidizing process, can improve pseudocumene oxidation productive rate.The present invention, for the production of trimellitic anhydride, has the advantage that catalyst life is long, catalyst amount is few, equipment corrosion is little, equipment investment is few, safety coefficient is high and energy consumption is low.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 ~ 5 optionally contrasts form with the TMB conversion ratio in comparative example 1 ~ 2 and TMA.
Detailed description of the invention
Further illustrating the present invention below in conjunction with embodiment, but the scope of protection of present invention comprises the scope being not limited to embodiment statement.
Embodiment 1
For the catalyst that trimellitic anhydride is produced, its raw material comprises following components by weight percent:
Heteropoly acid 1 part
Metal oxide 0.1 part
CNT 0.45 part
Metal oxide is nano level V
2o
5, TiO
2, MnO and CoO mixture, particle diameter 40 ~ 70nm, wherein V
2o
5with TiO
2between mol ratio be mol ratio between 1:0.95, MnO and CoO be 1:1.05), [V
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:1.
Heteropoly acid is Dawson structure heteropoly acid; CNT is SWCN.
The preparation method of this catalyst, carries out as follows:
1) by hydro-thermal reaction, heteropoly acid is disperseed immobilized to metal oxide particle surface, thus form metal-heteropoly acid compound; Hydrothermal temperature is 100 DEG C, and the reaction time is 12h;
2) make metal-heteropoly acid compound load to carbon nano tube surface by the hydroxyl of single tube-surface, extruded, forming shape is cylindrical, spherical, annular, cloverleaf pattern, honeycombed or bird-nest-shaped.Be preferably tooth spherical, then roasting obtains metal-heteropoly acid compound load carbon nano-tube catalyst.Sintering temperature is 150 DEG C, and roasting time is 15h.
This catalyst can be used for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.Specifically can synthesize trimellitic anhydride as follows:
1) metal obtained after roasting-heteropoly acid compound load carbon nano-tube catalyst is fixed on oxidation reaction tower catalyst fixed bed on, multi-layer catalyst layer is set on catalyst fixed bed; The voidage of catalyst layer successively increases from top to bottom along the direction of described simulation model for mixing gases flows;
2) raw material pseudocumene is first by flash of steam device, make it be heated to 200 DEG C, and flash distillation obtains gaseous state pseudocumene;
3) gaseous state pseudocumene and oxygen-containing gas mixing (volume ratio is 1:6) are passed into oxidation reaction tower, in mixed gas, oxygen quality content is 10%; Control at 5 ~ 10h in the mass space velocity of pseudocumene
-1, temperature is at 150 DEG C, and pressure is at 1.0MPa, and oxygen-containing gas is oxygen;
Mass space velocity=material quality flow (unit: kgh in the present embodiment and following examples and comparative example
-1)/catalyst quality (unit: kg).
4) in oxidation reaction tower, mist is step by step through each layer catalyst layer, and part gaseous state pseudocumene oxidation reaction also dehydration generates vaporific trimellitic anhydride;
5) mixture containing gaseous state pseudocumene and vaporific trimellitic anhydride passes in solid phase trap continuously, carries out trapping and obtain trimellitic anhydride finished product at 140 DEG C.
Embodiment 2
For the catalyst that trimellitic anhydride is produced, its raw material comprises following components by weight percent:
Heteropoly acid 1 part
Metal oxide 0.3 part
CNT 0.55 part
Metal oxide is nano level V
2o
5, TiO
2, MnO and CoO mixture, particle diameter 40 ~ 70nm, wherein V
2o
5with TiO
2between mol ratio be mol ratio between 1:1.05, MnO and CoO be 1:0.95, [V
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:3.
Heteropoly acid is Dawson structure heteropoly acid; CNT is SWCN.
This continuous vapour phase oxidation process produces the preparation method of the catalyst of trimellitic anhydride, carries out as follows:
1) by hydro-thermal reaction, heteropoly acid is disperseed immobilized to metal oxide particle surface, thus form metal-heteropoly acid compound; Hydrothermal temperature is 300 DEG C, and the reaction time is 3h;
2) make metal-heteropoly acid compound load to carbon nano tube surface by the hydroxyl of single tube-surface, extruded, forming shape is cylindrical, and then roasting obtains metal-heteropoly acid compound load carbon nano-tube catalyst.Sintering temperature is 350 DEG C, and roasting time is 5h.
This catalyst can be used for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.Specifically can synthesize trimellitic anhydride as follows:
1) metal obtained after roasting-heteropoly acid compound load carbon nano-tube catalyst is fixed on oxidation reaction tower catalyst fixed bed on, multi-layer catalyst layer is set on catalyst fixed bed; The voidage of catalyst layer successively increases from top to bottom along the direction of described simulation model for mixing gases flows;
2) raw material pseudocumene first obtains gaseous state pseudocumene by flash of steam device;
3) gaseous state pseudocumene and oxygen-containing gas mixing (volume ratio is 1:6) are passed into oxidation reaction tower; Control at 10h in the mass space velocity of pseudocumene
-1, temperature is at 200 DEG C, and pressure is at 2MPa, and oxygen-containing gas is oxygen; In mixed gas, oxygen quality content is 20%;
4) in oxidation reaction tower, mist is step by step through each layer catalyst layer, and part gaseous state pseudocumene oxidation reaction also dehydration generates vaporific trimellitic anhydride;
5) mixture containing gaseous state pseudocumene and vaporific trimellitic anhydride passes in solid phase trap continuously, carries out trapping and obtain trimellitic anhydride finished product at 160 DEG C.
Embodiment 3
For the catalyst that trimellitic anhydride is produced, its raw material comprises following components by weight percent:
Heteropoly acid 1 part
Metal oxide 0.3 part
CNT 0.45 part
Metal oxide is nano level V
2o
5, TiO
2, MnO and CoO mixture, particle diameter 40 ~ 70nm, wherein V
2o
5with TiO
2between mol ratio be mol ratio between 1:1, MnO and CoO be 1:1, [V
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:2.
Heteropoly acid is Dawson structure heteropoly acid; CNT is SWCN.
This continuous vapour phase oxidation process produces the preparation method of the catalyst of trimellitic anhydride, carries out as follows:
1) by hydro-thermal reaction, heteropoly acid is disperseed immobilized to metal oxide particle surface, thus form metal-heteropoly acid compound; Hydrothermal temperature is 200 DEG C, and the reaction time is 6h;
2) make metal-heteropoly acid compound load to carbon nano tube surface by the hydroxyl of single tube-surface, extruded, forming shape is cylindrical, spherical, annular, cloverleaf pattern, honeycombed or bird-nest-shaped.Be preferably tooth spherical, then roasting obtains metal-heteropoly acid compound load carbon nano-tube catalyst.Sintering temperature is 250 DEG C, and roasting time is 10h.
This catalyst can be used for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.Specifically can synthesize trimellitic anhydride as follows:
1) metal obtained after roasting-heteropoly acid compound load carbon nano-tube catalyst is fixed on oxidation reaction tower catalyst fixed bed on, multi-layer catalyst layer is set on catalyst fixed bed; The voidage of catalyst layer successively increases from top to bottom along the direction of described simulation model for mixing gases flows;
2) raw material pseudocumene first obtains gaseous state pseudocumene by flash of steam device;
3) gaseous state pseudocumene and oxygen-containing gas mixing (volume ratio is 1:6) are passed into oxidation reaction tower; Control at 7.5h in the mass space velocity of pseudocumene
-1, temperature is at 200 DEG C; Pressure is at 1.4MPa; In mixed gas, oxygen quality content is 15%;
4) in oxidation reaction tower, mist is step by step through each layer catalyst layer, and part gaseous state pseudocumene oxidation reaction also dehydration generates vaporific trimellitic anhydride;
5) mixture containing gaseous state pseudocumene and vaporific trimellitic anhydride passes in solid phase trap continuously, carries out trapping and obtain trimellitic anhydride finished product at 150 DEG C.
Embodiment 4
For the catalyst that trimellitic anhydride is produced, its raw material comprises following components by weight percent:
Heteropoly acid 1 part
Metal oxide 0.2 part
CNT 0.5 part
Metal oxide is nano level V
2o
5, TiO
2, MnO and CoO mixture, particle diameter 40 ~ 70nm, wherein V
2o
5with TiO
2between mol ratio be 1:(0.95 ~ 1.05), the mol ratio between MnO and CoO is 1:(0.95 ~ 1.05), [V
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:(1 ~ 3).
Heteropoly acid is Dawson structure heteropoly acid; CNT is SWCN.
The preparation method of this catalyst, carries out as follows:
1) by hydro-thermal reaction, heteropoly acid is disperseed immobilized to metal oxide particle surface, thus form metal-heteropoly acid compound; Hydrothermal temperature is 100 ~ 300 DEG C, and the reaction time is 3 ~ 12h;
2) make metal-heteropoly acid compound load to carbon nano tube surface, be squeezed into honeycombed by the hydroxyl of single tube-surface, then roasting obtains metal-heteropoly acid compound load carbon nano-tube catalyst.Sintering temperature is 300 DEG C, and roasting time is 8h.
This catalyst can be used for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.Specifically can synthesize trimellitic anhydride as follows:
1) metal obtained after roasting-heteropoly acid compound load carbon nano-tube catalyst is fixed on oxidation reaction tower catalyst fixed bed on, multi-layer catalyst layer is set on catalyst fixed bed; The voidage of catalyst layer successively increases from top to bottom along the direction of described simulation model for mixing gases flows;
2) raw material pseudocumene first obtains gaseous state pseudocumene by flash of steam device;
3) gaseous state pseudocumene and oxygen-containing gas mixing (volume ratio is 1:6) are passed into oxidation reaction tower; Control at 5 ~ 10h in the mass space velocity of pseudocumene
-1, temperature is at 160 ~ 170 DEG C; Pressure 1.4 ~ 1.6MPa; Oxygen-containing gas is preferably air, and in mixed gas, oxygen quality content is 10%;
4) in oxidation reaction tower, mist is step by step through each layer catalyst layer, and part gaseous state pseudocumene oxidation reaction also dehydration generates vaporific trimellitic anhydride;
5) mixture containing gaseous state pseudocumene and vaporific trimellitic anhydride passes in solid phase trap continuously, carries out trapping and obtain trimellitic anhydride finished product at 140 ~ 160 DEG C.
Embodiment 5
For the catalyst that trimellitic anhydride is produced, it obtains as follows:
Step one, the preparation of metal-heteropoly acid composite feedstock.
In reactor, add (weight portion) 1 part of Dawson structure heteropoly acid, 0.1 ~ 0.3 part of metal oxide successively, this metal oxide comprises nano level V
2o
5, TiO
2, MnO, CoO, particle diameter 40 ~ 70nm, wherein, V
2o
5with TiO
2between mol ratio be mol ratio between 1:1, MnO and CoO be 1:1, [V
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:3; Separately add 4 parts of deionized waters, ultrasonic disperse 0.5h, stir, under 100 ~ 300 DEG C of conditions, hydro-thermal reaction 3 ~ 12h, obtained metal-heteropoly acid compound.
Step 2, the preparation of metal-heteropoly acid compound load carbon nano-tube catalyst.
0.5 part of CNT and 3 parts of deionized waters are added in the metal-heteropoly acid composite feedstock of step one, ultrasonic disperse 2h, stir, concentrated, mediate, extruding makes it shaping, and forming shape can be cylindrical, spherical, annular, cloverleaf pattern, tooth are spherical, honeycombed or bird-nest-shaped.Then at 150 ~ 350 DEG C of roasting 5 ~ 15h, metal-heteropoly acid compound load carbon nano-tube catalyst is obtained.
0.5 part of SWCN and 3 parts of deionized waters are joined in above-mentioned obtained metal-heteropoly acid composite feedstock, stirs, ultrasonic disperse 2h, concentrated, mediate.Then tooth spherical (sphere diameter 25mm, tooth depth 15mm) granular solids is squeezed into.At 300 DEG C, carry out air roasting within 5 hours, obtain final metal-heteropoly acid compound load carbon nano-tube catalyst.
This catalyst can be used for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.Production process can be carried out as follows:
1) take pseudocumene as raw material, be heated to 200 DEG C by flash of steam device and reach vapor state, produce gaseous state pseudocumene;
2) gaseous state pseudocumene and air mixing (volume ratio is 1:6) are passed into the oxidation reaction tower containing composite catalyst fixed bed afterwards continuously, control at 5 ~ 10h in the mass space velocity of pseudocumene
-1, the voidage of catalyst layer increases step by step along in the direction that described admixture of gas flows from top to bottom multistep.Gaseous state pseudocumene is when temperature 220 DEG C, and pressure is carry out the oxidation reaction also vaporific state trimellitic anhydride of dehydration generation step by step under 1.5MPa condition;
3) pass into temperature continuously containing the mixture of gaseous state pseudocumene and vaporific trimellitic anhydride and obtain trimellitic anhydride finished product in the solid phase trap of 140 DEG C.Catalyst energy continuous production more than 1000 hours.
Below for adopting the contrast test of Mn-Co system or V-Ti system gaseous oxidation continuous seepage trimellitic anhydride:
Comparative example 1
The method of gaseous oxidation continuous seepage trimellitic anhydride, carry out according to the following steps:
Catalyst preparation process:
0.1 part of MnO and 0.1 part CoO is joined successively in the reactor containing 1 part of Dawson structure heteropoly acid and 4 parts of deionized waters, stir, ultrasonic disperse 0.5h.Under 200 DEG C of conditions, hydro-thermal 12h, obtained metal load type heteropoly acid raw material.0.5 part of SWCN and 3 parts of deionized waters are joined in above-mentioned obtained metal-heteropoly acid composite feedstock, stirs, ultrasonic disperse 2h, concentrated, mediate.Then tooth spherical (sphere diameter 25mm, tooth depth 15mm) granular solids is squeezed into.At 300 DEG C, carry out air roasting within 5 hours, obtain final metal-heteropoly acid compound load carbon nano-tube catalyst.
Production process:
1, take pseudocumene as raw material, be heated to 200 DEG C by flash of steam device and reach vapor state, produce gaseous state pseudocumene;
2, gaseous state pseudocumene and air mixture (volume ratio is 1:6) are passed into the oxidation reaction tower containing composite catalyst fixed bed continuously, control at 5h in the mass space velocity of pseudocumene
-1, the voidage of catalyst layer increases step by step along in the direction that described admixture of gas flows from top to bottom multistep.Gaseous state pseudocumene is when temperature 220 DEG C, and pressure is carry out the oxidation reaction also vaporific trimellitic anhydride of dehydration generation step by step under 1.5MPa condition;
3, pass into temperature continuously containing the mixture of gaseous state pseudocumene and vaporific trimellitic anhydride and obtain trimellitic anhydride finished product in the solid phase trap of 160 DEG C.
Comparative example 2
The method of gaseous oxidation continuous seepage trimellitic anhydride, has following steps:
Catalyst preparation process:
By 0.1 part of V
2o
5, 0.1 part of TiO
2join in the reactor containing 1 part of Dawson structure heteropoly acid and 4 parts of deionized waters successively, stir, ultrasonic disperse 0.5h.Under 200 DEG C of conditions, hydro-thermal 12h, obtained metal load type heteropoly acid raw material.0.5 part of SWCN and 3 parts of deionized waters are joined in above-mentioned obtained metal-heteropoly acid composite feedstock, stirs, ultrasonic disperse 2h, concentrated, mediate.Then tooth spherical (sphere diameter 25mm, tooth depth 15mm) granular solids is squeezed into.At 300 DEG C, carry out air roasting within 5 hours, obtain final metal-heteropoly acid compound load carbon nano-tube catalyst.
Production process:
1, take pseudocumene as raw material, be heated to 200 DEG C by flash of steam device and reach vapor state, produce gaseous state pseudocumene;
2, gaseous state pseudocumene and air mixture (volume ratio is 1:6) are passed into the oxidation reaction tower containing composite catalyst fixed bed continuously, control at 5h in the mass space velocity of pseudocumene
-1, the voidage of catalyst layer increases step by step along in the direction that described admixture of gas flows from top to bottom multistep.Gaseous state pseudocumene is when temperature 220 DEG C, and pressure is carry out the oxidation reaction also vaporific trimellitic anhydride of dehydration generation step by step under 1.5MPa condition;
3, pass into temperature continuously containing the mixture of gaseous state pseudocumene and vaporific trimellitic anhydride and obtain trimellitic anhydride finished product in the solid phase trap of 160 DEG C.
The catalyst performance of the continuous vapour phase oxidation process production trimellitic anhydride of the present invention's synthesis is evaluated as follows:
As shown in Figure 1, known by the contrast test data of embodiment 1 ~ 5 and comparative example 1 ~ 2, adopt the technique of Catalyst Production trimellitic anhydride of the present invention compared with domestic and international existing liquid phase (or gas phase) air oxidation process technique, there is pseudocumene conversion ratio high, the advantage that catalyst life is long, catalyst amount is few, equipment corrosion is little, equipment investment is few, safety coefficient is high and energy consumption is low.
The present invention is not limited to above-described embodiment; on the basis of technical scheme disclosed by the invention; those skilled in the art is according to disclosed technology contents; do not need performing creative labour just can make some to some technical characteristics wherein to replace and distortion, these are replaced and are out of shape all in protection scope of the present invention.
Claims (10)
1., for the catalyst that trimellitic anhydride is produced, it is characterized in that its raw material comprises following components by weight percent:
Heteropoly acid 1 part
Metal oxide 0.1 ~ 0.3 part
CNT 0.45 ~ 0.55 part
Described metal oxide is nano level V
2o
5, TiO
2, MnO and CoO mixture, particle diameter 40 ~ 70nm, wherein V
2o
5with TiO
2between mol ratio be 1:(0.95 ~ 1.05), the mol ratio between MnO and CoO is 1:(0.95 ~ 1.05), [V-
2o
5+ TiO
2] and [MnO+CoO] between mol ratio be 1:(1 ~ 3).
2. the catalyst produced for trimellitic anhydride according to claim 1, is characterized in that described heteropoly acid is Dawson structure heteropoly acid.
3. the catalyst produced for trimellitic anhydride according to claim 2, is characterized in that described CNT is SWCN.
4., for a preparation method for the catalyst of trimellitic anhydride production, it is characterized in that comprising the steps:
1) by hydro-thermal reaction, heteropoly acid is disperseed immobilized to metal oxide particle surface, thus form metal-heteropoly acid compound;
2) make metal-heteropoly acid compound load to carbon nano tube surface by the hydroxyl of single tube-surface, extruded, then roasting obtains metal-loaded by heteropoly acid carbon nano-tube catalyst.
5. the preparation method of catalyst produced for trimellitic anhydride according to claim 4, when it is characterized in that extruded, forming shape is cylindrical, spherical, annular, cloverleaf pattern, tooth are spherical, honeycombed or bird-nest-shaped.
6. the preparation method of the catalyst for trimellitic anhydride production according to claim 4, it is characterized in that hydrothermal temperature is 100 ~ 300 DEG C, the reaction time is 3 ~ 12h; Sintering temperature is 150 ~ 350 DEG C, and roasting time is 5 ~ 15h.
7. the purposes of the catalyst for trimellitic anhydride production according to claim 1, is characterized in that this catalyst is for pseudocumene gas phase continuous oxidation synthesis trimellitic anhydride.
8. the purposes of the catalyst for trimellitic anhydride production according to claim 1, is characterized in that synthesizing trimellitic anhydride as follows:
1) metal obtained after roasting-heteropoly acid compound load carbon nano-tube catalyst is fixed on oxidation reaction tower catalyst fixed bed on, multi-layer catalyst layer is set on catalyst fixed bed;
2) raw material pseudocumene first obtains gaseous state pseudocumene by flash of steam device;
3) gaseous state pseudocumene and oxygen-containing gas mixing are passed into oxidation reaction tower; Control at 5 ~ 10h in the mass space velocity of pseudocumene
-1, temperature is at 150 ~ 220 DEG C, and pressure is at 1.0 ~ 2.0MPa; In mixed gas, oxygen quality content is 10 ~ 20%; Described mass space velocity=material quality flow (unit: kgh
-1)/catalyst quality (unit: kg);
4) in oxidation reaction tower, mist is step by step through each layer catalyst layer, and part gaseous state pseudocumene oxidation reaction also dehydration generates vaporific trimellitic anhydride;
5) mixture containing gaseous state pseudocumene and vaporific trimellitic anhydride passes in solid phase trap continuously, carries out trapping and obtain trimellitic anhydride finished product at 140 ~ 160 DEG C.
9. the purposes of the catalyst for trimellitic anhydride production according to claim 8, is characterized in that the voidage of catalyst layer successively increases from top to bottom along the direction of described simulation model for mixing gases flows.
10. the purposes of the catalyst for trimellitic anhydride production according to claim 8, is characterized in that described oxygen-containing gas is air or oxygen.
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| CN110449112A (en) * | 2019-09-04 | 2019-11-15 | 江苏正丹化学工业股份有限公司 | A kind of pseudocumene continuous oxidation reaction device |
| CN110560112A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for preparing trimellitic anhydride |
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| CN110560115A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing trimellitic anhydride |
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