CN108097282A - A kind of catalyst for being used to prepare phthalic anhydride and its preparation method and application - Google Patents
A kind of catalyst for being used to prepare phthalic anhydride and its preparation method and application Download PDFInfo
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- CN108097282A CN108097282A CN201711349884.1A CN201711349884A CN108097282A CN 108097282 A CN108097282 A CN 108097282A CN 201711349884 A CN201711349884 A CN 201711349884A CN 108097282 A CN108097282 A CN 108097282A
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
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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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- 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
- B01J27/19—Molybdenum
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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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
- B01J27/228—Silicon carbide with phosphorus, arsenic, antimony or bismuth
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The present invention relates to a kind of catalyst for being used to prepare phthalic anhydride and its preparation method and application, and phthalic anhydride is prepared especially suitable for ortho-xylene or naphthalene gaseous oxidation.A kind of catalyst for being used to prepare phthalic anhydride, the catalyst includes active component, the active component, by mass percentage, it is formed by 0.01~20% heteropolyacid salt and with the oxide of surplus or salt, wherein, the heteropolyacid salt is the combination of one or both arbitrary proportion in the Tricesium dodecatungstophosphate of keggin structures, phosphomolybdic acid caesium；The oxide is V2O5、TiO2、Sb2O3、P2O5、Cs2O、Fe2O3、WO2、MoO3、SnO2Or Ag2At least one of O.Catalyst provided by the invention reduces the hot(test)-spot temperature of reaction by the decomposition slow releasing function of heteropolyacid salt and to the adjustment effect of acidity of catalyst, improves the selectivity of catalyst, extends catalyst life.
Description
Technical field
The present invention relates to a kind of catalyst for being used to prepare phthalic anhydride and its preparation method and application, especially suitable for adjacent diformazan
Benzene or naphthalene gaseous oxidation prepare phthalic anhydride.
Background technology
Phthalic anhydride is a kind of important Organic Chemicals, is mostly prepared with ortho-xylene or naphthalene catalytic gas phase oxidation, used
Catalyst active component based on vanadic anhydride and titanium dioxide.In catalyst technology development for many years, people attempt
Various metals, nonmetallic oxide and salt (not including heteropolyacid salt) improve catalyst performance.ZL97119198.0 is situated between
Continued a kind of production phthalic anhydride catalyst, and active ingredient is vanadic anhydride, titanium dioxide, phosphorus pentoxide, five oxidations two
Niobium and rubidium oxide.Load is 60-80g/ standard cubic meter air, and phthalic anhydride weight yield is 106-116%.ZL03153293.4 is situated between
Continued a kind of preparation method of phthalic anhydride, active ingredient be in addition to vanadic anhydride, titanium dioxide alkali metal,
The compound of the elements such as antimony, phosphorus, niobium.Weight yield 114-115%, 440-450 DEG C of hot(test)-spot temperature.
ZL200710176583.3 describes a kind of benzene anhydride catalyst and preparation method thereof, and active ingredient is five oxidations two
Vanadium, titanium dioxide, phosphorus pentoxide, niobium pentaoxide, antimony oxide, cesium sulfate etc..Weight yield 115%, hot(test)-spot temperature
440-450℃.CA102958605A discloses a kind of multi-layer catalyst for being used to manufacture phthalic anhydride, and active component is with before
The patent in face has no difference.Adjacent benzene load is up to 80-100g/ standard cubic meter air, and weight yield is in 110-111%, hot spot
Temperature is below 450 DEG C.CA102612446A discloses a kind of catalyst for preparing carboxylic acid anhydrides, introduces metaantimmonic acid vanadium to replace three oxygen
Change two antimony, adjacent benzene load 80g-100g/ standard cubic meters, for weight yield between 114-115%, hot(test)-spot temperature is down to 425 DEG C
Below.More than patent, load be in current phthalic anhydride technology it is above the average on, hot(test)-spot temperature is totally higher, only there are one patent
Below 425 DEG C, and do not refer to catalyst life.
The content of the invention
The problems such as present invention is low for load and product yield, and hot(test)-spot temperature is high provides a kind of production phthalic anhydride catalysis
Agent, using multistage filling process.It is intended to improve load and product yield, reduces hot(test)-spot temperature, improve catalyst stability, extend
Catalyst life.Catalyst provided by the invention, including carrier and active ingredient two parts.Carrier is by talcum, carborundum, oxidation
The inert materials such as aluminium are made；Active ingredient is made of the oxide and salt of vanadium, titanium, antimony, phosphorus, caesium, iron, tungsten, molybdenum, silver etc., especially
It is heteropolyacid salt Tricesium dodecatungstophosphate or phosphomolybdic acid caesium；And certain binding agent is added in active ingredient, in favor of load.In the present invention
The heteropolyacid salt of introducing has many effects, and catalyst first can effectively adjust the acid of catalyst by heteropolyacid salt
Property, and then the absorption on a catalyst of reactant and product and desorption process are effectively adjusted, so as to effectively adjust
Catalyst it is active and selective, reduce the hot(test)-spot temperature of reaction, improve the stability of catalyst, and extend the longevity of catalyst
Life；Second is that catalyst life is extended by the slow releasing function of heteropolyacid salt.Simultaneously using multistage filling process, catalyst is lived
Property, hotspot's distribution it is more reasonable, stability enhancing.
A kind of catalyst for being used to prepare phthalic anhydride, the catalyst include active component, the active component, by quality hundred
Divide ratio, formed by 0.01~20% heteropolyacid salt and with the oxide of surplus,
Wherein, the heteropolyacid salt is one or both arbitrary proportion in the Tricesium dodecatungstophosphate of keggin structures, phosphomolybdic acid caesium
Combination；The oxide is V2O5、TiO2、Sb2O3、P2O5、Cs2O、Fe2O3、WO2、MoO3、SnO2Or Ag2At least one in O
Kind.
In above-mentioned technical proposal, preferably described active component, by mass percentage, by 0.5~15% heteropolyacid salt and with
The oxide composition of surplus.
In above-mentioned technical proposal, preferably described oxide is V2O5、TiO2、Sb2O3、P2O5、Cs2O、Fe2O3、WO2、MoO3、
SnO2Or Ag2O。
In above-mentioned technical proposal, the salt corresponding to the oxide corresponds to the nitrate of metal ion, chlorination for oxide
Salt or oxalates, the salt as corresponding to the oxide can be vanadyl oxalate, silver nitrate, ferric trichloride, stannous chloride etc..
Further, the catalyst is made of carrier, active component and binding agent, the carrier for talcum, carborundum,
Aluminium oxide, the active component are 10~30% in the load capacity on carrier.
" load capacity " of the present invention accounts for the mass percent of catalyst for active component.
Preferably, the binding agent is acrylic acid and maleic acid is 3 by weight:The mixture of 1 composition.
Further, the dosage of the binding agent allows active component to be preferably fixed on carrier, preferably its
Load capacity is the 15~30% of vehicle weight.
Preferably, the Tricesium dodecatungstophosphate and phosphomolybdic acid caesium are by cesium carbonate and corresponding heteropoly acid in molar ratio 1~3:1 closes
Into.
It is a further object of the present invention to provide the preparation methods of above-mentioned catalyst.
A kind of preparation method for the catalyst for being used to prepare phthalic anhydride, the described method includes following processing steps：
1) processing of carrier：Carrier removes irregular or broken particle, deionized water cleaning is dried standby by screening
With；
2) slurry preparation：Phosphotungstic acid or phosphomolybdic acid are first added in ethanol water, after stirring evenly by cesium carbonate dropwise
It is added drop-wise in the solution of phosphotungstic acid or phosphomolybdic acid, when stirring 12 is small；Salt corresponding to required oxide or oxide is added to
In above-mentioned solution；Addition sequence is first to add in soluble material, adds insoluble material afterwards；Binding agent is eventually adding, is carried out abundant
It stirs and is ground, form suspension or mixture of viscous form；
3) drying is sprayed：Carrier is put into flush coater, carrier is heated to above 100 DEG C by hot wind, starts to spray, is controlled
Temperature is 100~130 DEG C during system spraying；Slurry is sprayed to after atomization on the carrier stirred；Hot wind causes slurry carrying
Cure on body, until active ingredient reaches expected component, that is, complete the preparation of catalyst.
In above-mentioned preparation method, in the step 2), the volumetric concentration of the ethanol water is 50%.
In above-mentioned preparation method, in the step 3), carrier is heated to slightly above 100 DEG C by hot wind, preferably
It is heated to 100~130 DEG C.
It is yet another object of the invention to provide the applications of above-mentioned catalyst.
A kind of method for preparing phthalic anhydride is the method that catalytic gas phase oxidation prepares phthalic anhydride using ortho-xylene or naphthalene as raw material,
Used catalyst includes active component, the active component, by mass percentage, by 0.01~20% heteropolyacid salt and and surplus
Oxide composition,
Wherein, the heteropolyacid salt is one or both arbitrary proportion in the Tricesium dodecatungstophosphate of keggin structures, phosphomolybdic acid caesium
Combination；The oxide is V2O5、TiO2、Sb2O3、P2O5、Cs2O、Fe2O3、WO2、MoO3、SnO2Or Ag2At least one in O
Kind, the reaction carries out in tubular fixed-bed reactor, and the catalyst carries out multistage filling in reactor, and concrete mode is such as
Under：
Type of feed one：Catalyst is six layers, and from entrance to outlet, the molar ratio of heteropolyacid salt is in each section of catalyst
0.01~0.1:0.1~0.2:0.2~0.3:0.3~0.7:0.1~0.2:0.4~0.6；
Type of feed two：Catalyst is six layers, and from entrance to outlet, the molar ratio of heteropolyacid salt is in each section of catalyst
0.01~0.1:0.1~0.2:0.1~0.2:0.2~0.3:0.4~0.6:0.3~0.7.
Beneficial effects of the present invention are：Heteropolyacid salt of the present invention, is keggin structures, and P elements are in structure
Center.Compared in phosphorus pentoxide, the touch opportunity of phosphorus and reactant is reduced, but the salt acidic of heteropolyacid salt compares oxide
Acidity it is strong very much, compensate for the effect of phosphorus from another point of view.The heteropolyacid salt is during catalyst use, with pole
Slow resolution of velocity is the higher phosphorus pentoxide of activity and tungsten metal oxide, the bleed rate phase with active ingredient
Match somebody with somebody, be finally reached holding catalyst performance, extend catalyst life.In addition the acidity of heteropoly acid can be very good to adjust catalyst
Acidity, improve the activity and selectivity of catalyst, reduce the hot(test)-spot temperature of reaction, reduce the loss of active component, extend
Catalyst life.The catalyst service life, it is contemplated that extend 1~2 year than the typical catalyst service life.In addition, catalyst of the present invention
Using multistage filling process, activity, hotspot's distribution are more reasonable, stability enhancing, and are amenable to larger frequency driving and parking test.
Design hotspot location is located at 100~140cm sections below entrance, the smooth-going of hot spot curve；Load is stood up to 100~120g/ standards
Square rice, gas weight yield are up to more than 117~118, and hot spot is below 430 DEG C, excellent product quality.
Specific embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is conventional method unless otherwise specified；The reagent and material, such as
Without specified otherwise, commercially obtain.
Catalyst bed activity distribution mode described in following implementations is as follows：
Type of feed one：Catalyst is six layers, and from entrance to outlet, the molar ratio of heteropolyacid salt is in each section of catalyst
0.01~0.1:0.1~0.2:0.2~0.3:0.3~0.7:0.1~0.2:0.4~0.6；
Type of feed two：Catalyst is six layers, and from entrance to outlet, the molar ratio of heteropolyacid salt is in each section of catalyst
0.01~0.1:0.1~0.2:0.1~0.2:0.2~0.3:0.4~0.6:0.3~0.7.
Bed height is distributed：3~10cm of first layer, 30~120cm of the second layer, 40~120cm of third layer, the 4th layer 30~
80cm, 30~80cm of layer 5,20~80cm of layer 6, total catalyst height 345cm.
Embodiment 1
The processing of carrier：Carrier is the talcum ring of outer diameter 7*7*4mm, and carrier is dried standby by screening, deionized water cleaning
With.
Slurry preparation：
(1) 2.50g phosphoric acid tungsten is added in the 50% of 700mL ethanol water, 0.28g carbonic acid is then added dropwise
Caesium, when stirring 12 is small under room temperature.
(2) 17.1g vanadyl oxalates are added in the solution prepared in (1), adds 6.58g silver nitrates, 158g titanium dioxides
Titanium, 10g organic binder bond (acrylic acid：Maleic acid=3:1, weight ratio, other embodiment is same) and 120mL formamides.Stirring
Uniformly, and using Homogenizing pump homogeneous 30 minutes under 4000rpm, suspension is formed.
Spray drying：
The 1000g carriers handled well are put into flush coater, carrier is heated to 105 DEG C by hot wind, starts to spray, are controlled
Temperature is 110 DEG C during spraying.Slurry is sprayed to after atomization on the carrier stirred.Spraying, which finishes, to be continued to heat 1min, is gone out
Material, obtains catalyst prod A.
Comparative example 1
(1) 2.50g phosphotungstic acids in embodiment 1 are replaced with into 0.11g ammonium dihydrogen phosphates, 1.71g ammonium metatungstates (before and after replacement
The mass conservation of phosphorus, wolfram element, similarly hereinafter).
(2) sequentially added in the water of 700ml ammonium dihydrogen phosphate, ammonium metatungstate, vanadyl oxalate, silver nitrate, titanium dioxide,
Organic binder bond and formamide, and using Homogenizing pump homogeneous 30 minutes under 4000rpm, form suspension.
(3) sprayed, dried according to the spraying method in embodiment 1.Obtain catalyst prod a.
Embodiment 2
Preparation method is respectively with embodiment 1, the amount of each component：50% ethanol water 750ml, phosphomolybdic acid 6.54g,
Cesium carbonate 1.68g, vanadyl oxalate 20.3g, silver nitrate 15.0g, titanium dioxide 168g, ferric trichloride 0.1g, antimony oxide
0.5g, stannous chloride 2.0g, binding agent 11g, formamide 120ml. obtain catalyst prod B.
Comparative example 2
6.54g phosphomolybdic acids in embodiment 2 are replaced with into 0.50g ammonium dihydrogen phosphates, 9.24g ammonium paramolybdates, other are the same as implementation
Example 2 prepares catalyst according to the method for comparative example 1, obtains catalyst prod b.
Embodiment 3
Preparation method is respectively with embodiment 1, the amount of each component：50% ethanol water 800ml, phosphotungstic acid 7.8g,
Phosphomolybdic acid 4.77g, cesium carbonate 2.36g, vanadyl oxalate 26.0g, titanium dioxide 180g, ferric trichloride 0.5g, antimony oxide
1.0g, stannous chloride 1.0g, binding agent 12g, formamide 120ml. obtain catalyst prod C.
Comparative example 3
By 7.8g phosphotungstic acids, 4.77g phosphomolybdic acids in embodiment 3 replace with 0.72g ammonium dihydrogen phosphates, 9.09g ammonium metatungstates,
6.74g ammonium paramolybdates, the other the same as in Example 3 prepare catalyst according to the method for comparative example 1, obtain catalyst prod c.
Embodiment 4
Preparation method is respectively with embodiment 1, the amount of each component：50% ethanol water 850ml, phosphotungstic acid 7.8g,
Phosphomolybdic acid 13.52g, cesium carbonate 5.44g, vanadyl oxalate 35.0g, titanium dioxide 180g, ferric trichloride 2.5g, antimony oxide
13.5g, binding agent 12g, formamide 120ml. obtain catalyst prod D.
Comparative example 4
7.8g phosphotungstic acids, 13.52g phosphomolybdic acids in embodiment 4 are replaced with into 1.39g ammonium dihydrogen phosphates, 9.08g metatungstic acids
Ammonium, 19.11g ammonium paramolybdates, the other the same as in Example 4 prepare catalyst according to the method for comparative example 1, obtain catalyst prod d.
Embodiment 5
Preparation method is respectively with embodiment 1, the amount of each component：50% ethanol water 800ml, phosphotungstic acid
17.04g, phosphomolybdic acid 10.8g, cesium carbonate 6.35g, vanadyl oxalate 35.0g, titanium dioxide 180g, ferric trichloride 1.5g, three oxidations
Two antimony 3.5g, binding agent 12g, formamide 120ml. obtain catalyst prod E.
Comparative example 5
17.04g phosphotungstic acids, 10.8g phosphomolybdic acids in embodiment 5 are replaced with into 1.59g ammonium dihydrogen phosphates, 20.4g metatungstic acids
Ammonium, 19.85g ammonium paramolybdates, the other the same as in Example 5 prepare catalyst according to the method for comparative example 1, obtain catalyst prod e.
Embodiment 6
Preparation method is respectively with embodiment 1, the amount of each component：50% ethanol water 800ml, phosphotungstic acid 3.8g,
Phosphomolybdic acid 13.52g, cesium carbonate 4.48g, vanadyl oxalate 30.0g, titanium dioxide 180g, ferric trichloride 1.5g, antimony oxide
3.5g, binding agent 12g, formamide 120ml. obtain catalyst prod F.
Comparative example 6
3.8g phosphotungstic acids, 13.52g phosphomolybdic acids in embodiment 5 are replaced with into 1.21g ammonium dihydrogen phosphates, 4.43g metatungstic acids
Ammonium, 19.10g ammonium paramolybdates, other same embodiments 6, prepare catalyst according to the method for comparative example 1, obtain catalyst prod f.
Evaluate embodiment 1
The processability for carrying out preparing phthalic anhydride to catalyst prepared by above method using ortho-xylene as raw material is evaluated, below
It is evaluation embodiment and evaluation comparative example.
By catalyst A-F form a system, arrange in alphabetical order from the inlet to the outlet, filling height be successively 3cm,
32cm, 120cm, 50cm, 60cm, 80cm, total catalyst height 345cm.
Reaction raw materials are ortho-xylene, load for 43~95 grams per cubic metres of air (specifically be respectively 43,53,65,
75th, 85,95), air mass flow is 4.0 standard cubic meters, carries out driving and parking experiment.Evaluating catalyst uses single tube reactor, instead
Bore is answered to be packed into reaction tube each layer catalyst of different performance by different height for 25mm and test.Test number
Be shown in Table 1 according to record, phthalic anhydride keep in high yield, high-quality, hot(test)-spot temperature stablizes, and hotspot location is kept well, instead after stationary phase
The multiple every Con trolling index of parking is without significant change.Below 425 DEG C of highest hot spot, still have and continue to increase load space.
Evaluate embodiment 2
Catalyst packing is the same as evaluation example 1.In load 93g/m3Carry out secondary driving and parking experiment.Data are shown in Table 1.Items control
Index is without significant change.
Evaluate comparative example 1
Catalyst a-f is formed into a system, is arranged in alphabetical order from the inlet to the outlet, filling height is distributed corresponding evaluation
Example 1.In load 43,53,65,75,85,95g/m3It carries out stopping running experience.Data are shown in Table 2.After stopping repeatedly, driving, yield has
Slightly downward trend, hot(test)-spot temperature omit ascendant trend, and hotspot location has the trend slightly moved down.Hot(test)-spot temperature has reached 445
DEG C, without the space for continuing increase load.
Evaluate comparative example 2
Catalyst packing is the same as evaluation example 2.In load 93g/m3Carry out secondary driving and parking experiment.Data are shown in Table 2.It is secondary to stop
Che Hou, catalyst performance are steady.
Evaluate embodiment 3
By catalyst A-F form a system, it is ABECFD to put in order from the inlet to the outlet, filling height be successively 3cm,
102cm, 50cm, 50cm, 60cm, 80cm, total catalyst height 345cm.It is the same evaluation example 1 of declaratives.Load 43,55,
66、76、83、93g/m3It carries out stopping running experience.Data are shown in Table 3.Phthalic anhydride keep in high yield, high-quality, hot(test)-spot temperature stablize, heat
Point position is kept well after stationary phase, and every Con trolling index that stops repeatedly is without significant change.
Evaluate comparative example 3
Catalyst a-f is formed into a system, it is abecfd to put in order from the inlet to the outlet, and filling height is distributed correspondence and comments
Valency example 3.In load 43,55,66,76,83,93g/m3It carries out stopping running experience.Data are shown in Table 4.Phthalic anhydride in high yield, high-quality.
After stopping vehicle repeatedly, yield has slightly downward trend, and hot(test)-spot temperature omits ascendant trend, and hotspot location has the trend slightly moved down.
Evaluate embodiment 4
Catalyst packing is the same as evaluation example 3.In load 96g/m3Carry out secondary driving and parking experiment.Data are shown in Table 3.Items control
Index is without significant change.
Evaluate comparative example 4
Catalyst packing is the same as evaluation example 3.In load 96g/m3Carry out secondary driving and parking experiment.Data are shown in Table 4.It is secondary to stop
Che Hou, catalyst performance are steady.
Evaluation summary：The catalyst for introducing heteropolyacid salt shows some superiority.Embodiment evaluating catalyst, yield
More than 118-119%, below 425 DEG C of hot(test)-spot temperature, hotspot's distribution rationally, stablize, load also has the space further improved.And
Comparative example is evaluated, and yield averagely declines 2 percentage points, and hot(test)-spot temperature is up to 445 DEG C, and after repeatedly stopping vehicle, hotspot location moves down
Trend, load have reached vertex.2 driving and parking of two kinds of catalyst after induction period, all performance are steady.
Table 1
Table 2
Table 3
Table 4
Claims (5)
1. a kind of catalyst for being used to prepare phthalic anhydride, it is characterised in that：The catalyst includes active component, the activearm
Point, by mass percentage, formed by 0.01~20% heteropolyacid salt and with the salt corresponding to the oxide or oxide of surplus,
Wherein, the heteropolyacid salt is the group of one or both arbitrary proportion in the Tricesium dodecatungstophosphate of keggin structures, phosphomolybdic acid caesium
It closes；The oxide is V2O5、TiO2、Sb2O3、P2O5、Cs2O、Fe2O3、WO2、MoO3、SnO2Or Ag2At least one of O.
2. catalyst according to claim 1, it is characterised in that：The catalyst is by carrier, active component and binding agent
Composition, the carrier is talcum, carborundum, aluminium oxide, and the active component is 10~30% in the load capacity on carrier.
3. catalyst according to claim 1, it is characterised in that：The Tricesium dodecatungstophosphate and phosphomolybdic acid caesium by cesium carbonate and
Corresponding heteropoly acid in molar ratio 1~3:1 synthesis, forms and loading process is synchronized with the preparation of slurry and sprays dried
Journey.
4. the preparation method of catalyst described in claim 1, it is characterised in that：The described method includes following processing steps：
1) processing of carrier：Carrier removes irregular or broken particle, deionized water cleaning is dried for standby by screening；
2) slurry preparation：Phosphotungstic acid or phosphomolybdic acid are first added in ethanol water, cesium carbonate is added dropwise dropwise after stirring evenly
Into the solution of phosphotungstic acid or phosphomolybdic acid, when stirring 12 is small；Salt corresponding to required oxide or oxide is added to above-mentioned
In solution；Addition sequence is first to add in soluble material, adds insoluble material afterwards；Binding agent is eventually adding, is sufficiently stirred
And be ground, form suspension or mixture of viscous form；
3) drying is sprayed：Carrier is put into flush coater, carrier is heated to above 100 DEG C by hot wind, starts to spray, control spray
Temperature is 100~130 DEG C during painting；Slurry is sprayed to after atomization on the carrier stirred；Hot wind causes slurry on carrier
Cure, until active ingredient reaches expected component, that is, complete the preparation of catalyst.
A kind of 5. method for preparing phthalic anhydride, it is characterised in that：It is using ortho-xylene or naphthalene as raw material, catalytic gas phase oxidation prepares benzene
The method of acid anhydride, used catalyst are catalyst described in claim 1, and the reaction carries out in tubular fixed-bed reactor, institute
It states catalyst and carries out multistage filling in reactor, concrete mode is as follows：
Type of feed one：Catalyst is six layers, and from entrance to outlet, the molar ratio of heteropolyacid salt is 0.01 in each section of catalyst
~0.1:0.1~0.2:0.2~0.3:0.3~0.7:0.1~0.2:0.4~0.6；
Type of feed two：Catalyst is six layers, and from entrance to outlet, the molar ratio of heteropolyacid salt is 0.01 in each section of catalyst
~0.1:0.1~0.2:0.1~0.2:0.2~0.3:0.4~0.6:0.3~0.7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112536053A (en) * | 2019-09-23 | 2021-03-23 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride from o-xylene and preparation method thereof |
| CN112642454A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride by oxidizing o-xylene and preparation method thereof |
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| CN1580050A (en) * | 2003-08-14 | 2005-02-16 | 中国石油化工股份有限公司 | Method for preparing phthalic anhydride |
| CN102941119A (en) * | 2012-11-17 | 2013-02-27 | 聊城大学 | Preparation method for silicon dioxide loading heteropoly cesium catalyst |
| CN104525231A (en) * | 2014-12-12 | 2015-04-22 | 大连龙想催化化学股份有限公司 | Hydrocarbon oxidation catalyst and preparation method thereof |
| WO2017085229A1 (en) * | 2015-11-19 | 2017-05-26 | Shell Internationale Research Maatschappij B.V. | Catalyst system and process for the production of glycols |
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| JPH01132574A (en) * | 1987-11-18 | 1989-05-25 | Mitsubishi Gas Chem Co Inc | Production of high-purity phthalic anhydride |
| CN1580050A (en) * | 2003-08-14 | 2005-02-16 | 中国石油化工股份有限公司 | Method for preparing phthalic anhydride |
| CN102941119A (en) * | 2012-11-17 | 2013-02-27 | 聊城大学 | Preparation method for silicon dioxide loading heteropoly cesium catalyst |
| CN104525231A (en) * | 2014-12-12 | 2015-04-22 | 大连龙想催化化学股份有限公司 | Hydrocarbon oxidation catalyst and preparation method thereof |
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| CN112536053A (en) * | 2019-09-23 | 2021-03-23 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride from o-xylene and preparation method thereof |
| CN112536053B (en) * | 2019-09-23 | 2023-09-08 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride from o-xylene and preparation method thereof |
| CN112642454A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride by oxidizing o-xylene and preparation method thereof |
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| CN108097282B (en) | 2020-08-28 |
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