CN101130535B - Method for producing phthallic anhydride - Google Patents
Method for producing phthallic anhydride Download PDFInfo
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- CN101130535B CN101130535B CN2006101126093A CN200610112609A CN101130535B CN 101130535 B CN101130535 B CN 101130535B CN 2006101126093 A CN2006101126093 A CN 2006101126093A CN 200610112609 A CN200610112609 A CN 200610112609A CN 101130535 B CN101130535 B CN 101130535B
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Abstract
The invention discloses a preparing method of ortho-phthalic anhydride, which is characterized by the following: choosing ortho-xylene and naphthalene as raw material; proceeding gas phase catalytic oxidation reaction; adopting two-phase, three-phase bed or four-phase bed V-Ti type accelerant; setting the accelerant as carrier material; coating catalytic activity matter with vanadic oxide and titanium oxide on the carrier; choosing compound from free alkali metal, Sb, P and Nb; adding as catalyst promoter. This invention can modify composite of the reacting rear gas, which can be used to organic chemical industry domain.
Description
Technical field
The present invention relates to the preparation method of Tetra hydro Phthalic anhydride, being specifically related to o-Xylol, naphthalene is that raw material carries out the method that gas phase catalytic oxidation reaction prepares Tetra hydro Phthalic anhydride.
Background technology
With o-Xylol and/or naphthalene is raw material fixed bed catalytic oxidation system phthalic anhydride, generally adopts V-Ti type catalyzer, promptly with V
2O
5And TiO
2Be catalytic active substance, and add that to be selected from least a compound of being made up of in the group basic metal, Sb, P, Nb, Ag, Zr, W, Au, Sn, Bi etc. be promotor, use the atresia inert support material, catalytic active substance to be generally 0.02～2 millimeter lamelliform, is coated on the carrier of inertia atresia and the preparation catalyzer.
But the catalyzer of prior art can not be satisfactory at the aspects such as yield of catalytic activity, the generation that suppresses by product or selectivity, life of catalyst and phthalic anhydride.Along with the increase of naphthalene in the unstripped gas or o-Xylol concentration, these problems are also just more serious, from economically, need make the concentration of naphthalene or o-Xylol surpass its lower limits of explosion.
When improving the o-Xylol input concentration,, phthalic anhydride productive rate and quality product are produced great effect because catalyst activity and stability are not good enough.At present the catalyzer that uses is to carry out catalytic oxidation under higher temperature, less gas feed amount and lower naphthalene or o-Xylol concentration, can reduce the generation of by product, but the condition that is adopted makes that the productive rate of phthalic anhydride is not high.Because in the phthalic anhydride production process, the raw material o-Xylol has occupied the main composition of production cost, require the yield of higher phthalic anhydride aborning, promptly cut down the consumption of raw materials.Owing to the poor stability of catalyzer, phthalic anhydride yield and quality product show relatively poor result in the middle and later periods of catalyzer operation during life of catalyst simultaneously, make the Financial cost of device operation improve.
In order to overcome above-mentioned defective, numerous investigators has done deep research to the preparation method and the catalyzer thereof of phthalic anhydride, has proposed the method and the catalyzer thereof of many improvement naphthalenes or o-Xylol catalytic gas phase oxidation.
BASF AG is at US.6,362, in 345, a kind of preparation method of Tetra hydro Phthalic anhydride is disclosed, this method is included in the fixed bed, at elevated temperatures, with the mixed gas of molecule-containing keto with use the coated catalysts that is contained in the mutual superposition section at least, catalytic gas phase oxidation o-Xylol and/or naphthalene.This catalyzer comprises the catalytically active metal oxides layer that is coated on the inert support material, ingress section catalyzer I accounts for 25～75% of beds volume, vanadium oxide content is 1～10% in the active substance of catalyzer I, anatase titanium dioxide content is 80～90%, 1～10% weisspiessglanz, and the Cesium compound that adds 0.05～1.0%, the lower section catalyst II accounts for 75～25% of beds volume, vanadium oxide content is 1～10% in the active substance of catalyst II, anatase titanium dioxide content is 80～90%, 1～10% weisspiessglanz, and the Cesium compound that adds 0.01～1.0%, form two sections bed catalyst beds, produce phthalic anhydride.
Disclose a kind of catalyzer among the WO2004000455, used a kind of Vanadium Pentoxide in FLAKES (V that contains 2～15 weight %
2O
5), the stannic oxide of 1～15% weight, the anatase titanium dioxide of 70～97 weight %, at least a basic metal of～5% weight % or the catalyzer of other metallic compounds, being used for catalytic gas phase oxidation o-Xylol and/or naphthalene has catalytic activity and phthalic anhydride selectivity preferably.
US6,586,361 and CN1314827 a kind of painting catalyst that is used for the catalytic vapor phase oxidation of aromatic hydrocarbons is disclosed, this catalyzer comprises the vanadium oxide of determining content on the carrier of inertia atresia, titanium dioxide, Cesium compound, the catalytic activity composition of phosphorus compound and weisspiessglanz, wherein the catalyst activity composition paints two or multilayer, with respect to internal layer or each internal layer, outer field weisspiessglanz content low 50～100%, wherein the amount of the catalytic activity composition of internal layer or each internal layer is 10～90% weight of catalytic activity amount of composition, this catalyzer can be used to prepare carboxylic acid and/or acid anhydrides, especially Tetra hydro Phthalic anhydride.
Catalyzer used in the industrial production generally needs higher temperature of molten salt, just can guarantee the conversion fully and the phthalic anhydride quality of o-Xylol.If the reduction temperature of molten salt when raising feeds intake concentration, o-Xylol can occur and transform not exclusively, intermediate product is many, brings serious irritating smell.More seriously under higher salt temperature, if the material concentration in the raising reaction atmosphere, then reaction aggravation, heat release is strong, cause the beds hot(test)-spot temperature too high and the deep oxidation reaction takes place, reduced the yield of phthalic anhydride, the serious catalyst deactivation that will make influences work-ing life of catalyzer.
Though catalyzer has been carried out many improvement,, still there are some defectives in present employed catalyzer.Usually the phthalic anhydride yield of industrializeding catalyst is 108～110%, obviously descends along with prolonging catalyst activity duration of service; Because the catalytic activity of catalyzer is lower, the reacting salt bath temperature is higher, and it is limited to improve the concentration that feeds intake.Even form by improving catalyzer, improve the charging capacity of o-Xylol, be difficult to also guarantee that catalyzer has good phthalic anhydride selectivity and quality product.Especially under the higher load condition of o-Xylol, for example, when o-Xylol concentration reaches 80g/m
3When above, the o-Xylol transformation efficiency reduces, reaction generates o-Xylol content height in the gas, and phthalide, phenylformic acid, phenyl aldehyde, tolyl acid, tolyl aldehyde and lemon acid anhydride etc. also have remarkable increase, makes the phthalic anhydride yield descend, influence the phthalic anhydride quality product, and because intermediate product increases, tail gas moderate stimulation gas content increases, and brings serious environmental issue, so the performance of catalyzer remains further to improve and improve, and particularly improves the thermostability and the selectivity of catalyzer.
Summary of the invention
The technical problem to be solved in the present invention is:
In order to overcome in the prior art catalyzer at o-Xylol concentration 80g/m
3The deficiency that exists when above, the preparation method who the purpose of this invention is to provide a kind of Tetra hydro Phthalic anhydride, this method is used unique catalyzer, this catalyzer has higher catalytic activity, selectivity and stability under higher load condition, with high yield and high quality of production phthalic anhydride and long-term operation, can obviously reduce major impurity phthalide content in the product, and fully reduced intermediate product with irritating smell, improve quality product, overcome the big problem of exhaust emissions pungency in the phthalic anhydride production.
Technical scheme of the present invention is:
A kind of preparation method of Tetra hydro Phthalic anhydride, this method is a raw material with o-Xylol and/or naphthalene, prepare Tetra hydro Phthalic anhydride with the gaseous oxidation catalyzed reaction of molecule-containing keto, use fixed-bed reactor, material from up to down flows in the reaction tubes bed, adopts two sections, three sections or four sections bed loading catalysts; The catalyzer of each section bed filling includes: the solid support material of inertia atresia is coated with one deck and contains Vanadium Pentoxide in FLAKES V on carrier
2O
5With titanium dioxide TiO
2Catalytic active substance,
The catalyzer of each section bed filling all is selected from following catalyzer I～IV, one of 4 kinds of catalyzer, and with bed sections from top to bottom, the label of catalyzer is from small to large;
But do not comprise the catalyzer I and the catalyst II combination of two sections beds, and the catalyzer III and the combination of catalyzer IV that do not comprise two sections beds.
All the other array modes of two sections beds can, four kinds of array modes of three sections beds also can, four sections beds have only only array mode.
The catalyzer I: its preparation raw material comprises following component: weight percent is 3%～10% V
2O
5, weight percent is 0.20%～2.0% antimonous oxide Sb
2O
3, with Cs
2O meter weight percent is 0.01%～1.0% cesium sulfate, with P
2O
5The meter weight percent is 0～0.5% primary ammonium phosphate, with Nb
2O
5The meter weight percent is 0～1.0% the niobium oxalate and the anatase titanium dioxide of surplus to 100%; Promptly niobium oxalate can be contained, also niobium oxalate can be do not contained.
Catalyst II: its preparation raw material comprises following component: weight percent is 5%～10% V
2O
5, and V
2O
5Weight content be V in the catalyzer I
2O
51～1.5 times of weight content; Weight content is 0.5%～4% Sb
2O
3, and Sb
2O
3Weight content be Sb in the catalyzer I
2O
31.5～2 times of weight content; Anatase titanium dioxide with surplus to 100%;
The catalyzer III: its preparation raw material comprises following component: weight percent is 7～15% V
2O
5, and V
2O
5Weight content be V in the catalyst II
2O
51～1.3 times of weight content; Weight content is 2%～6% Sb
2O
3, and Sb
2O
3Weight content be Sb in the catalyst II
2O
31.25～1.5 times of weight content; Anatase titanium dioxide with surplus to 100%;
The catalyzer IV: the catalyst activity material contains: weight percent is 8～20% V
2O
5, and V
2O
5Weight content be V in the catalyzer III
2O
51～1.25 times of weight content; Weight content is 3%～9% Sb
2O
3, and Sb
2O
3Weight content be Sb in the catalyzer III
2O
31.0～1.5 times of weight content; Anatase titanium dioxide with surplus to 100%.
Above-mentioned catalyzer can be further preferred:
Described catalyzer I: its preparation raw material comprises following component: weight percent is 3～10% V
2O
5, weight percent is 0.5～1% Sb
2O
3, with Cs
2O meter weight percent is 0.2%～0.5% cesium sulfate, with P
2O
5The meter weight percent is 0.2%～0.4% primary ammonium phosphate, with Nb
2O
5The meter weight percent is 0.4%～0.6% the niobium oxalate and the anatase titanium dioxide of surplus to 100%; Adopt spraying method, immersion process for preparing to form.
Described catalyst II: its preparation raw material comprises following component: weight percent is 5～10% V
2O
5, weight percent is 1%～3% Sb
2O
3And the anatase titanium dioxide of surplus to 100%; Adopt spraying method, immersion process for preparing to form.
Described catalyzer III: its preparation raw material comprises following component: weight percent is 7～15% V
2O
5, weight percent is 2.5%～5.5% Sb
2O
3And the anatase titanium dioxide of surplus to 100%; Adopt spraying method, immersion process for preparing to form.
Described catalyzer IV: its preparation raw material comprises following component: weight percent is 8～20% V
2O
5, weight percent is 4.5%～6.5% Sb
2O
3And the anatase titanium dioxide of surplus to 100%; Adopt spraying method, immersion process for preparing to form.
The combination of two kinds, three kinds or four kinds catalyzer of employing of the present invention realizes, special with the catalyzer I as first section catalyzer in the multistage bed, it is the catalyzer of reaction gas inlet section, catalyzer III and catalyzer IV can be used as reaction gas outlet section catalyzer, catalyst II and catalyzer III are used as the interlude catalyzer, with two kinds, three kinds or four kinds of catalyzer in accordance with regulations order fill in the single tube reaction unit.
When adopting two sections bed loading catalysts, the admission space of epimere bed catalyzer is 50%～70% of a total fill able volume, all the other volume filling hypomere bed catalyzer; Epimere bed catalyzer is selected from catalyzer I or catalyst II, and hypomere bed catalyzer is selected from catalyzer III or catalyzer IV.I+III, I+IV, II+III, II+IV can be arranged, four kinds of array configurations; But can not use the combination of catalyzer I+II, III+IV.
When adopting three sections bed loading catalysts, the admission space of epimere bed catalyzer is 40%～70% of a total fill able volume, and the admission space of stage casing bed catalyzer is 40～20% of a total fill able volume, all the other volume filling hypomere bed catalyzer; Epimere bed catalyzer is selected from catalyzer I or catalyst II, and stage casing bed catalyzer is selected from catalyst II or catalyzer III, and hypomere bed catalyzer is selected from catalyzer III or catalyzer IV.II+III+IV, I+III+IV, I+II+IV, I+II+III can be arranged, four kinds of array configurations.
When adopting four sections bed loading catalysts, from top to bottom, the admission space of first section bed catalyzer is 30～50% of a total fill able volume, the admission space of second section bed catalyzer is 10～20% of a total fill able volume, the admission space of the 3rd section bed catalyzer is 30～40% of a total fill able volume, and all the other volumes load the 4th section bed catalyzer; Each section bed order loading catalyst I～IV promptly has only a kind of array configuration of I+II+III+IV.
When adopting two sections bed loading catalysts, the transformation efficiency of epimere bed catalyzer is 70%～90%, and the transformation efficiency of hypomere bed catalyzer reaches 100%;
When adopting three sections bed loading catalysts, the transformation efficiency of epimere bed catalyzer is 50%～85%, and the transformation efficiency of stage casing bed catalyzer reaches 85%～90%, and the transformation efficiency of hypomere bed catalyzer reaches 100%;
When adopting four sections bed loading catalysts, from top to bottom, the transformation efficiency of first section bed catalyzer is 50%～75%, the transformation efficiency of second section bed catalyzer reaches 75%～95%, the transformation efficiency of the 3rd section bed catalyzer reaches 95%～98%, and the transformation efficiency of the 4th section bed catalyzer reaches 100%.
In each catalyzer of described catalyzer I～IV, described anatase titanium dioxide TiO
2Specific surface area be 10m
2/ g～50m
2/ g, the hole of aperture 10nm～50nm accounts for 60%～70%, and pore volume is 0.15ml/g～0.35ml/g; Described anatase titanium dioxide TiO
2Particle diameter be 0.1 μ m～0.4 μ m.
Described anatase titanium dioxide TiO
2Specific surface area be preferably 18m
2/ g～24m
2/ g.
In described each catalyzer, solid support material is selected from a kind of in talcum, fused SiC, fused aluminum oxide, agglomerating talcum, pure aluminium silicate, quartz, the pottery, preferably adopts the agglomerating talcum; The porosity of carrier is less than 10%, or non-porous support;
The shape of inert support has no particular limits, as long as have good heat and mass transfer performance, is generally annular, cylindrical, sphere or ball shape, is preferably annular;
The carrier outside diameter is 3mm～12mm; Be preferably 5mm～8mm;
The height of annular, cylindrical vector is 4mm～7mm.
Catalyzer I～IV of the present invention can adopt conventional disclosed method preparation, be about to the salt or the oxide dissolution of catalyst activity component and various promotors or be suspended in deionized water and the mixture of organic solvent in, form solution or suspension.The ratio of mixture of water and solvent is 2%～20% (weight), and organic solvent can adopt C
1～C
4Alcohol, ethanamide, methane amide, urea etc.Above-mentioned solution or suspension adding are made in the suspension with titanium dioxide, carried out thorough mixing and further emulsification.
Can directly above-mentioned emulsion be immersed in carrier surface; Perhaps in coating pan, carrier is preheating to 100 ℃～300 ℃, above-mentioned emulsion is sprayed on the carrier.Activity substance content on carrier reaches 3%～30%, and preferred 5%～15%.Catalyzer was calcined 2～12 hours down in 400～450 ℃ in oxidizing atmosphere, prepared catalyzer.Promptly can adopt pickling process, also can adopt spraying method to prepare catalyzer.
The invention has the beneficial effects as follows:
Catalyzer of the present invention has higher catalytic activity, selectivity and stability under higher load condition, with high yield and high quality of production phthalic anhydride and long-term operation, can obviously reduce major impurity phthalide content in the product, and fully reduced intermediate product with irritating smell, improve quality product, overcome the big problem of exhaust emissions pungency in the phthalic anhydride production.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Prepare catalyzer I, II, III and IV as follows, and it is carried out performance evaluation.
(1) with 75.48g oxalic acid vanadyl, the 5.74g cesium sulfate, the 5.03g niobium oxalate, the 240mL methane amide is mixed with solution, with 765.6g titanium dioxide, 8.44g antimonous oxide mixing and emulsifying be uniform suspension.Suspension is sprayed on the carrier, and the activity substance content to carrier reaches 12.0%, is prepared into V-Ti-Cs-Sb-Nb catalyzer I.
(2) with 100.22g oxalic acid vanadyl, the 1.13g cesium sulfate, the 12.45g niobium oxalate, the 5.74g primary ammonium phosphate, the 240mL methane amide is mixed with solution, with 696g titanium dioxide, 18.60g antimonous oxide mixing and emulsifying be uniform suspension.Suspension is sprayed on the carrier, and the activity substance content to carrier reaches 14.0%, is prepared into the V-Ti-Cs-Sb-P-Nb catalyst II.
(3) with 104.04g oxalic acid vanadyl, the 0.57g cesium sulfate, the 6.07g niobium oxalate, the 5.74g primary ammonium phosphate, the 240mL methane amide is mixed with solution, with 696g titanium dioxide, 25.05g antimonous oxide mixing and emulsifying be uniform suspension.Suspension is sprayed on the carrier, and the activity substance content to carrier reaches 15.0%, is prepared into V-Ti-Cs-Sb-P-Nb catalyzer III.
(4) with 114.35g oxalic acid vanadyl, the 1.131g cesium sulfate, the 12.15g niobium oxalate, the 5.74g primary ammonium phosphate, the 240mL methane amide is mixed with solution, with 696g titanium dioxide, 36.55g antimonous oxide mixing and emulsifying be uniform suspension.Suspension is sprayed on the carrier, and the activity substance content to carrier reaches 15.0%, is prepared into V-Ti-Cs-Sb-P-Nb catalyzer IV.
With o-Xylol and/or naphthalene is raw material, uses the catalyzer according to the said process preparation to be prepared phthalic anhydride:
Employed single tube reactor is made by boiler steel, and internal diameter is 25mm, and pipe range 2000～4000mm, catalyst packing height are 1200～3700mm.Reaction product is collected in the capturing device, in exit, reaction tubes lower end thief hole is set.It is the heat exchange body that reaction tubes adopts pump circulation mobile fused salt outward, and reaction heat is derived by fused salt.Reaction bed temperature and temperature of molten salt thermocouple measurement.
Embodiment 1
Being two sections beds, catalyzer I, catalyzer III are formed catalystic converter system, is 25mm at internal diameter, pipe range is in the reaction tubes of 4000mm, epimere bed loading catalyst I, and loading height is 1700mm, hypomere bed loading catalyst III, loading height is 1500mm.Fused salt is mobile in the reaction tubes external jacket shifts out reaction heat by forcing, and adopts multiple spot thermocouple measurement temperature of reaction in reaction tubes.
In air flow quantity is 4Nm
3/ h, o-Xylol concentration is 83g/Nm
3, when salt temperature was 357 ℃, the yield of phthalic anhydride was 113%.The catalyzer hot(test)-spot temperature is 430 ℃～440 ℃, and hotspot location is positioned at beds 500mm～600mm place from top to bottom.By sampling analysis, reaction generates in the gas, and phthalide content is 0.05%.
Embodiment 2
Be two sections beds, catalyst II, catalyzer IV are formed catalystic converter system, reaction unit is with embodiment 1.Epimere bed loading catalyst I, loading height is 1700mm, hypomere bed loading catalyst III, loading height is 1500mm.In air flow quantity is 4Nm
3/ h, o-Xylol concentration is 81g/Nm
3, when salt temperature was 356 ℃, the yield of phthalic anhydride was 113%.The catalyzer hot(test)-spot temperature is 430 ℃～445 ℃, and hotspot location is positioned at beds 500mm～600mm place from top to bottom.Reaction generates in the gas, and phthalide content is 0.05%.
Embodiment 3
Be three sections beds, catalyzer I, catalyst II, catalyzer III are formed catalyst system, reaction unit is with embodiment 1.Epimere bed loading catalyst I, loading height is 1300mm, stage casing bed loading catalyst II, loading height is 800mm, hypomere bed loading catalyst III, loading height is 1300mm.In air flow quantity is 4Nm
3/ h, o-Xylol concentration is 85g/Nm
3, when salt temperature was 355 ℃, the yield of phthalic anhydride was 114%.The catalyzer hot(test)-spot temperature is 440～450 ℃, and hotspot location is positioned at beds 500～600mm place from top to bottom.Reaction generates in the gas, and phthalide content is 0.05%.
Embodiment 4
Be three sections beds, catalyzer I, catalyzer III, catalyzer IV are formed catalystic converter system, reaction unit is with embodiment 1.Epimere bed loading catalyst I, loading height is 1700mm, stage casing bed loading catalyst III, loading height is 1200mm, hypomere bed loading catalyst IV, loading height is 500mm.In air flow quantity is 4Nm
3/ h, o-Xylol concentration is 90g/Nm
3, when salt temperature was 355 ℃, the yield of phthalic anhydride was 115%.The catalyzer hot(test)-spot temperature is 440～450 ℃, and hotspot location is positioned at beds 500～600mm place from top to bottom.Reaction generates in the gas, and phthalide content is 0.04%.
Embodiment 5
Be three sections beds, catalyst II, catalyzer III, catalyzer IV are formed catalyst system, reaction unit is with embodiment 1.Epimere bed loading catalyst II, loading height is 1300mm, stage casing bed loading catalyst III, loading height is 800mm, hypomere bed loading catalyst IV, loading height is 1300mm.In air flow quantity is 4Nm
3/ h, o-Xylol concentration is 85g/Nm
3, when salt temperature was 355 ℃, the yield of phthalic anhydride was 114%.The catalyzer hot(test)-spot temperature is 440～450 ℃, and hotspot location is positioned at beds 500～600mm place from top to bottom.Reaction generates in the gas, and phthalide content is 0.05%.
Embodiment 6
Be four sections beds, catalyzer I, catalyst II, catalyzer III, catalyzer IV are formed catalystic converter system, reaction unit is with embodiment 1.Above first section bed loading catalyst I, loading height is 1300mm, first section bed loading catalyst II, loading height is 700mm, the 3rd section bed loading catalyst III, and loading height is 1000mm, below the 4th section bed loading catalyst IV, loading height is 500mm.In air flow quantity is 4Nm
3/ h, o-Xylol concentration is 95g/Nm
3, when salt temperature was 355 ℃, the yield of phthalic anhydride was 115%.The catalyzer hot(test)-spot temperature is 440～450 ℃, and hotspot location is positioned at beds 500～600mm place from top to bottom, and reaction generates in the gas, and phthalide content is 0.03%.
Phthalic anhydride preparation method test-results table of the present invention
Claims (6)
1. the preparation method of a Tetra hydro Phthalic anhydride, this method is that the gaseous oxidation catalyzed reaction of raw material and molecule-containing keto prepares Tetra hydro Phthalic anhydride with o-Xylol and/or naphthalene, use fixed-bed reactor, material from up to down flows in the reaction tubes bed, adopts two sections, three sections or four sections bed loading catalysts; The catalyzer of each section bed filling includes: the solid support material of inertia atresia is coated with one deck and contains Vanadium Pentoxide in FLAKES V on carrier
2O
5With titanium dioxide TiO
2Catalytic active substance, it is characterized in that:
The catalyzer of each section bed filling all is selected from following catalyzer I～IV, one of 4 kinds of catalyzer, and with bed sections from top to bottom, the label of catalyzer is from small to large; But do not comprise the catalyzer I and the catalyst II combination of two sections beds, and the catalyzer III and the combination of catalyzer IV that do not comprise two sections beds;
Catalyzer I: with 75.48g oxalic acid vanadyl, 5.74g cesium sulfate, 5.03g niobium oxalate, the 240mL methane amide, be mixed with solution, with 765.6g titanium dioxide, 8.44g antimonous oxide mixing and emulsifying be uniform suspension, suspension is sprayed on the carrier, activity substance content to carrier reaches 12.0%, is prepared into V-Ti-Cs-Sb-Nb catalyzer I;
Catalyst II: with 100.22g oxalic acid vanadyl, 1.13g cesium sulfate, 12.45g niobium oxalate, 5.74g primary ammonium phosphate, the 240mL methane amide is mixed with solution, with 696g titanium dioxide, 18.60g antimonous oxide mixing and emulsifying be uniform suspension, suspension is sprayed on the carrier, and the activity substance content to carrier reaches 14.0%, is prepared into the V-Ti-Cs-Sb-P-Nb catalyst II;
Catalyzer III: with 104.04g oxalic acid vanadyl, 0.57g cesium sulfate, 6.07g niobium oxalate, 5.74g primary ammonium phosphate, the 240mL methane amide is mixed with solution, with 696g titanium dioxide, 25.05g antimonous oxide mixing and emulsifying be uniform suspension, suspension is sprayed on the carrier, and the activity substance content to carrier reaches 15.0%, is prepared into V-Ti-Cs-Sb-P-Nb catalyzer III;
Catalyzer IV: with 114.35g oxalic acid vanadyl, 1.131g cesium sulfate, 12.15g niobium oxalate, 5.74g primary ammonium phosphate, the 240mL methane amide is mixed with solution, with 696g titanium dioxide, 36.55g antimonous oxide mixing and emulsifying be uniform suspension, suspension is sprayed on the carrier, and the activity substance content to carrier reaches 15.0%, is prepared into V-Ti-Cs-Sb-P-Nb catalyzer IV.
2. the preparation method of Tetra hydro Phthalic anhydride according to claim 1 is characterized in that:
When adopting two sections bed loading catalysts, the admission space of epimere bed catalyzer is 50%～70% of a total fill able volume, all the other volume filling hypomere bed catalyzer;
When adopting three sections bed loading catalysts, the admission space of epimere bed catalyzer is 40%～70% of a total fill able volume, and the admission space of stage casing bed catalyzer is 40～20% of a total fill able volume, all the other volume filling hypomere bed catalyzer;
When adopting four sections bed loading catalysts, from top to bottom, the admission space of first section bed catalyzer is 30～50% of a total fill able volume, the admission space of second section bed catalyzer is 10～20% of a total fill able volume, the admission space of the 3rd section bed catalyzer is 30～40% of a total fill able volume, and all the other volumes load the 4th section bed catalyzer.
3. the preparation method of Tetra hydro Phthalic anhydride according to claim 1 is characterized in that:
In each catalyzer of described catalyzer I～IV, described anatase titanium dioxide TiO
2Specific surface area be 10m
2/ g～50m
2/ g, the hole of aperture 10nm～50nm accounts for 60%～70%, and pore volume is 0.15ml/g～0.35ml/g; Described anatase titanium dioxide TiO
2Particle diameter be 0.1 μ m～0.4 μ m.
4. the preparation method of Tetra hydro Phthalic anhydride according to claim 3 is characterized in that:
Described anatase titanium dioxide TiO
2Specific surface area be 18m
2/ g～24m
2/ g.
5. the preparation method of Tetra hydro Phthalic anhydride according to claim 1 is characterized in that:
In described each catalyzer, solid support material is selected from a kind of in talcum, fused SiC, fused aluminum oxide, pure aluminium silicate, quartz, the pottery; The porosity of carrier is less than 10%, or non-porous support; Support shapes is annular, cylindrical, sphere or ball shape; The carrier outside diameter is 3mm～12mm; The height of annular, cylindrical vector is 4mm～7mm.
6. the preparation method of Tetra hydro Phthalic anhydride according to claim 5 is characterized in that:
Described solid support material is the agglomerating talcum, and support shapes is an annular, and the carrier outside diameter is 5mm～8mm.
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|---|---|---|---|
| CN2006101126093A CN101130535B (en) | 2006-08-25 | 2006-08-25 | Method for producing phthallic anhydride |
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|---|---|---|---|
| CN2006101126093A CN101130535B (en) | 2006-08-25 | 2006-08-25 | Method for producing phthallic anhydride |
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| CN101130535B true CN101130535B (en) | 2010-10-13 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012014154A1 (en) * | 2010-07-30 | 2012-02-02 | Basf Se | Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride |
| CN102008971B (en) * | 2010-10-19 | 2012-08-29 | 黑龙江省科学院石油化学研究院 | Preparation method of pyromellitic dianhydride catalyst |
| CN106699708B (en) * | 2015-11-12 | 2020-06-09 | 中国石油化工股份有限公司 | Method for producing phthalic anhydride |
| CN108794439B (en) * | 2017-05-02 | 2021-09-21 | 中国科学院大连化学物理研究所 | Preparation method of phthalide |
| CN107033047B (en) * | 2017-05-09 | 2019-03-26 | 濮阳宏业环保新材料股份有限公司 | A kind of stabilizer improving thiourea dioxide hydrothermal stability |
| CN110872265B (en) * | 2018-08-31 | 2021-09-21 | 中国石油化工股份有限公司 | Preparation method of phthalic anhydride |
| 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 |
| CN112547103B (en) * | 2019-09-26 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride by oxidation and preparation method thereof |
| CN112642453A (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 naphthalene oxidation 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 |
| CN114425380A (en) * | 2020-09-24 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing pyromellitic anhydride by oxidizing durene, preparation method and application |
| CN112608293B (en) * | 2020-12-16 | 2024-04-05 | 联欣环保科技(泰兴)有限公司 | Tail gas treatment method for phthalic anhydride production |
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