CN108640926A - A kind of method of industry anthracene selection hydro-oxidation coupling producing pyromellitic dianhydride - Google Patents
A kind of method of industry anthracene selection hydro-oxidation coupling producing pyromellitic dianhydride Download PDFInfo
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- CN108640926A CN108640926A CN201810375903.6A CN201810375903A CN108640926A CN 108640926 A CN108640926 A CN 108640926A CN 201810375903 A CN201810375903 A CN 201810375903A CN 108640926 A CN108640926 A CN 108640926A
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- anthracene
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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Abstract
A kind of industry anthracene selection adds the method for hydroxide coupling producing pyromellitic dianhydride, belongs to coal chemical industry and field of fine chemical.Anthracene obtains symmetrical octahydro anthracene by metal sulfide catalyst hydrofinishing combination noble metal catalyst selective hydrogenation reaction；Again using symmetrical octahydro anthracene as raw material, by metal oxide catalyst, with air oxidation, crystallization obtains pyromellitic acid anhydride.Selection hydrofinishing air oxidation coupling technique used herein handles industrial anthracene, obtains the pyromellitic acid anhydride of high added value.By selecting hydrofinishing to obtain symmetrical octahydro anthracene, it is raw material effectively to substitute durol, directly carries out the monomer pyromellitic acid anhydride that oxidation processes acquisition prepares polyimide resin with compressed air, increases economic efficiency.The present invention have it is simple for process, it is the low, high-environmental of energy consumption, with good investment, be conducive to deep processing on the spot and increase added value, the utilization for industry anthracene provides new approach, and with good economic efficiency and prospects for commercial application.
Description
Technical field
The invention belongs to coal chemical industries and field of fine chemical, and it is high to be related to a kind of industrial anthracene selection hydro-oxidation coupling system
The method of added value pyromellitic acid anhydride.
Background technology
Pyromellitic acid anhydride is mainly used for heat-resistant polymer-polyimide resin raw material, such as:Motor and cable it is resistance to
Thermal insulative pad or around packaging material, or it is used as substrate of flexible circuit board；For the heat-resisting high-tension cable of plasticizer-manufacture, resistance to hot polymerization
Vinyl chloride high quality artificial is removed from office；For epoxy curing agent, such as：Heat resistance is up to 200~250 DEG C of the instantaneous gluing of impact resistance
Agent；Delustering agent, the addition for powdery paints and surfactant or emulsifier, water treatment agent, metal inhibitor, leather retanning agent
Agent, the cryogenic property modifier of diesel oil, electronic photography tone improver and fire-resistant lubricants processed, dyestuff and polyester resin change
Property etc..
Pyromellitic acid anhydride is mainly aoxidized by vapor phase method with durol and is obtained at present, simple for process, can be saved de-
Water does not have to other oxidants (such as nitric acid, permanganic acid, chromic acid), is not required to urge necessary to liquid phase yet than air at anhydridization process
Agent separation process, and can continuous production, it is easy to accomplish automation mechanized operation.However, used raw material durene is expensive,
And be difficult to obtain, related process is monopolized with catalyst by external major company.Therefore, it is badly in need of exploring the cheap chemistry of a strip adoption
Raw material substitutes durol, and process simplification prepares the approach of high added value pyromellitic acid anhydride.
Anthracene is largely present in heavy crude and coal tar as a kind of typical condensed-nuclei aromatics.In addition, condensed-nuclei aromatics sheet
Body is a kind of carcinogen, seriously threatens human health.With the development of fine chemistry industry, demand of the people to fine chemicals
Increasingly increase, the symmetrical octahydro anthracene of hydrogenation products of wherein anthracene is a kind of important intermediate, the production of can effectively replace durol
Pyromellitic acid anhydride.For the above situation, we successfully develop a kind of industrial anthracene selection hydro-oxidation coupling and make equal benzene four
The hydrogenated refined, selection of industrial anthracene is hydrogenated to the symmetrical octahydro anthracene of high-quality by the method for formic acid dianhydride.What is obtained is symmetrical
Octahydro anthracene obtains the pyromellitic acid anhydride of high added value through gaseous oxidation again.
Invention content
The invention discloses a kind of method that industrial anthracene selection hydro-oxidation couples producing pyromellitic dianhydride, features
Be industrial anthracene is obtained into anthracene through the metal sulfide catalyst hydrofinishing removal wherein nitrogenous heteroatomic compound of sulfur-bearing, wherein
Anthracene is hydrogenated to symmetrical octahydro anthracene and by-product through solvent dilution through the fixed bed reactors selection equipped with noble metal catalyst,
Solvent recovery recycles after concentrated, and product obtains the symmetrical octahydro anthracene of high-quality after rectifying.The symmetrical octahydro anthracene obtained
Oxidation reaction occurs with compressed air through the fixed bed reactors equipped with metal oxide catalyst again, reaction product is crystallized to be obtained
To the pyromellitic acid anhydride of high added value.
Technical scheme of the present invention：
A kind of method of industry anthracene selection hydro-oxidation coupling producing pyromellitic dianhydride, steps are as follows：
(1) first by hydrofinishing tower of the industrial anthracene injection equipped with metal sulfide catalyst, reaction bed temperature control
System is between 180-300 DEG C, hydrogen partial pressure 5-15MPa, volume space velocity 0.5-4.0h- 1It is 300-1200 with hydrogen to oil volume ratio：1；
(2) obtained anthracene injects the fixed bed reactors equipped with noble metal catalyst through solvent dilution after hydrofinishing,
Reaction bed temperature controls between 100-200 DEG C, hydrogen partial pressure 2-7MPa, volume space velocity 0.5-2.0h- 1With hydrogen oil volume
Than for 300-1200：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery recycles, and product is through essence
The symmetrical octahydro anthracene of high-quality is obtained after evaporating；
(3) by the symmetrical octahydro anthracene obtained again through fixed bed reactors and compression sky equipped with metal oxide catalyst
Oxidation reaction occurs for gas, and reaction bed temperature controls between 380-440 DEG C, reaction pressure 0.15-0.3MPa, gas space velocity
4000-6000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction product is crystallized to obtain the equal benzene four of high added value
Formic acid dianhydride.
The metal sulfide catalyst of the present invention is with the SiO with double middle hole composite constructions2、Al2O3、TiO2Equal oxides
For carrier, using one or two or more kinds of compounds of the metal sulfide of VIII, the VIB such as nickel, cobalt, molybdenum, tungsten as active constituent.
The noble metal catalyst of the present invention is Rh/Al2O3、Pt/Al2O3、Pd/Al2O3、Ru/Al2O3、Rh/C、Pd/C、Ir/
Al2O3And Rh/SiO2In one or two or more kinds of compounds be active constituent.
The metal oxide catalyst of the present invention is with Al2O3For the V of carrier2O5、MoO3、TiO2One kind in equal oxides or
Two kinds or more compounds are active constituent.
Selection hydrofinishing-air oxidation coupling technique used herein handles industrial anthracene, obtains high additional
The pyromellitic acid anhydride of value.By selecting hydrofinishing to obtain symmetrical octahydro anthracene, it is raw material effectively to substitute durol, directly
Monomer-pyromellitic acid anhydride that oxidation processes acquisition prepares polyimide resin is carried out with compressed air, is increased economic efficiency.
The present invention have it is simple for process, it is the low, high-environmental of energy consumption, with good investment, be conducive to deep processing on the spot and increase added value, for industrial anthracene
Using providing new approach, and with good economic efficiency and prospects for commercial application.
Description of the drawings
A kind of process flow charts of industrial anthracene selection hydro-oxidation coupling producing pyromellitic dianhydride of Fig. 1
In figure：1 crude anthracene upgrading tower；2 rectifying columns；3 selections plus hydrogen tower；4 concentration towers；5 hydrogenation anthracene rectifying columns；
6 oxidizing towers；7 purifying columns；8 crystallizing tanks.
Specific implementation mode
Below in conjunction with attached drawing and technical solution, the specific implementation mode that further illustrates the present invention.
The injection of industrial anthracene is equipped with NiMoS/Al by embodiment 12O3The hydrofinishing tower of catalyst, at 180 DEG C, hydrogen partial pressure
5MPa, volume space velocity 0.5h- 1It is 300 with hydrogen to oil volume ratio：1 carries out hydrofinishing, and gained anthracene injects after decahydronaphthalene dilutes
Equipped with Rh/Al2O3Fixed bed reactors, reaction bed temperature control is at 100 DEG C, hydrogen partial pressure 7MPa, volume space velocity
0.5h- 1It is 1200 with hydrogen to oil volume ratio：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery is again
It utilizes, product obtains the symmetrical octahydro anthracene (purity of high-quality after rectifying>98%).The symmetrical octahydro anthracene obtained is again through being equipped with
V2O5-MoO3/TiO2-Al2O3With compressed air oxidation reaction, reaction bed temperature control occur for the fixed bed reactors of catalyst
System is at 380 DEG C, reaction pressure 0.3MPa, gas space velocity 4000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction production
Crystallized pyromellitic acid anhydride (the purity for obtaining high added value of object>98%).
The yield of symmetrical octahydro anthracene obtained by the present embodiment is 95wt%, and the yield of pyromellitic acid anhydride is 92wt%.
The injection of industrial anthracene is equipped with NiWS/Al by embodiment 22O3The hydrofinishing tower of catalyst, at 300 DEG C, hydrogen partial pressure
15MPa, volume space velocity 4h- 1It is 1200 with hydrogen to oil volume ratio：1 carries out hydrofinishing, and gained anthracene injects after decahydronaphthalene dilutes
Equipped with Pt/Al2O3Fixed bed reactors, reaction bed temperature control at 200 DEG C, hydrogen partial pressure 2MPa, volume space velocity 2h- 1
It is 300 with hydrogen to oil volume ratio：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery recycles, production
Product obtain the symmetrical octahydro anthracene (purity of high-quality after rectifying>95%).The symmetrical octahydro anthracene obtained is again through being equipped with V2O5-
PO5/TiO2-Al2O3With compressed air oxidation reaction occurs for the fixed bed reactors of catalyst, and reaction bed temperature control exists
440 DEG C, reaction pressure 0.15MPa, gas space velocity 6000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction product warp
Crystallization obtains the pyromellitic acid anhydride (purity of high added value>97%).
The yield of symmetrical octahydro anthracene obtained by the present embodiment is 90wt%, and the yield of pyromellitic acid anhydride is 89wt%.
The injection of industrial anthracene is equipped with CoMoS/Al by embodiment 32O3The hydrofinishing tower of catalyst, at 280 DEG C, hydrogen partial pressure
10MPa, volume space velocity 1h- 1It is 800 with hydrogen to oil volume ratio：1 carries out hydrofinishing, and gained anthracene injects after hexamethylene dilutes
Fixed bed reactors equipped with Rh/C, reaction bed temperature are controlled at 170 DEG C, hydrogen partial pressure 6MPa, volume space velocity 1h- 1With
Hydrogen to oil volume ratio is 600：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery recycles, product
The symmetrical octahydro anthracene (purity of high-quality is obtained after rectifying>95%).The symmetrical octahydro anthracene obtained is again through being equipped with V2O5-TiO2/
PO5-Al2O3With compressed air oxidation reaction occurs for the fixed bed reactors of catalyst, and reaction bed temperature is controlled at 400 DEG C,
Reaction pressure 0.2MPa, gas space velocity 5000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction product is crystallized to be obtained
To the pyromellitic acid anhydride (purity of high added value>99%).
The yield of symmetrical octahydro anthracene obtained by the present embodiment is 95wt%, and the yield of pyromellitic acid anhydride is 94wt%.
The injection of industrial anthracene is equipped with CoWS/Al by embodiment 42O3The hydrofinishing tower of catalyst, at 240 DEG C, hydrogen partial pressure
10MPa, volume space velocity 2h- 1It is 800 with hydrogen to oil volume ratio：1 carries out hydrofinishing, and gained anthracene injects after n-decane dilutes
Equipped with Ir/Al2O3Fixed bed reactors, reaction bed temperature control is at 170 DEG C, hydrogen partial pressure 5MPa, volume space velocity
1.5h- 1It is 500 with hydrogen to oil volume ratio：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery is sharp again
With product obtains the symmetrical octahydro anthracene (purity of high-quality after rectifying>92%).The symmetrical octahydro anthracene obtained is again through being equipped with
MoO3/TiO2-Al2O3With compressed air oxidation reaction occurs for the fixed bed reactors of catalyst, and reaction bed temperature control exists
380 DEG C, reaction pressure 0.10MPa, gas space velocity 4000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction product warp
Crystallization obtains the pyromellitic acid anhydride (purity of high added value>94%).
The yield of symmetrical octahydro anthracene obtained by the present embodiment is 93wt%, and the yield of pyromellitic acid anhydride is 90wt%.
The injection of industrial anthracene is equipped with NiMoWS/Al by embodiment 52O3The hydrofinishing tower of catalyst, at 260 DEG C, hydrogen partial pressure
8MPa, volume space velocity 1h- 1It is 600 with hydrogen to oil volume ratio：1 carries out hydrofinishing, and gained anthracene injects dress after decahydronaphthalene dilutes
There are the fixed bed reactors of Rh/C, reaction bed temperature to control at 120 DEG C, hydrogen partial pressure 6MPa, volume space velocity 0.8h- 1With
Hydrogen to oil volume ratio is 500：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery recycles, product
The symmetrical octahydro anthracene (purity of high-quality is obtained after rectifying>98%).The symmetrical octahydro anthracene obtained is again through being equipped with V2O5/TiO2-
Al2O3With compressed air oxidation reaction occurs for the fixed bed reactors of catalyst, and reaction bed temperature is controlled at 390 DEG C, reaction
Pressure 0.3MPa, gas space velocity 4000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction product is crystallized to obtain height
Pyromellitic acid anhydride (the purity of added value>98%).
The yield of symmetrical octahydro anthracene obtained by the present embodiment is 91wt%, and the yield of pyromellitic acid anhydride is 94wt%.
Claims (5)
1. a kind of method of industry anthracene selection hydro-oxidation coupling producing pyromellitic dianhydride, which is characterized in that steps are as follows：
(1) first by hydrofinishing tower of the industrial anthracene injection equipped with metal sulfide catalyst, reaction bed temperature control exists
Between 180-300 DEG C, hydrogen partial pressure 5-15MPa, volume space velocity 0.5-4.0h- 1It is 300-1200 with hydrogen to oil volume ratio：1；
(2) obtained anthracene is catalyzed through fixed bed reactors of the solvent dilution injection equipped with noble metal catalyst after hydrofinishing
Agent bed temperature controls between 100-200 DEG C, hydrogen partial pressure 2-7MPa, volume space velocity 0.5-2.0h- 1It is with hydrogen to oil volume ratio
300-1200：1, selection is hydrogenated to symmetrical octahydro anthracene and by-product, and concentrated rear solvent recovery recycles, and product is after rectifying
Obtain the symmetrical octahydro anthracene of high-quality；
(3) the symmetrical octahydro anthracene obtained is sent out through the fixed bed reactors equipped with metal oxide catalyst with compressed air again
Raw oxidation reaction, reaction bed temperature control between 380-440 DEG C, reaction pressure 0.15-0.3MPa, gas space velocity
4000-6000h- 1It is the symmetrical octahydro anthracene/m of 10g with air ratio3Air, reaction product is crystallized to obtain the equal benzene four of high added value
Formic acid dianhydride.
2. according to the method described in claim 1, it is characterized in that, the metal sulfide catalyst is multiple to have double mesoporous
Close the SiO of structure2、Al2O3、TiO2It is to live with one or two or more kinds of compounds of the metal sulfide of VIII, VIB for carrier
Property ingredient.
3. method according to claim 1 or 2, which is characterized in that the noble metal catalyst is Rh/Al2O3、Pt/
Al2O3、Pd/Al2O3、Ru/Al2O3、Rh/C、Pd/C、Ir/Al2O3And Rh/SiO2In one or two or more kinds of compounds be live
Property ingredient.
4. method according to claim 1 or 2, which is characterized in that the metal oxide catalyst is with Al2O3To carry
The V of body2O5、MoO3、TiO2In one or two or more kinds of compounds be active constituent.
5. according to the method described in claim 3, it is characterized in that, the metal oxide catalyst is with Al2O3For carrier
V2O5、MoO3、TiO2In one or two or more kinds of compounds be active constituent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115925716A (en) * | 2021-08-24 | 2023-04-07 | 中国石油化工股份有限公司 | Preparation method of pyromellitic dianhydride |
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