CN1108966A - Supported catalyst for preparing phthalic anhydride - Google Patents
Supported catalyst for preparing phthalic anhydride Download PDFInfo
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- CN1108966A CN1108966A CN94117515A CN94117515A CN1108966A CN 1108966 A CN1108966 A CN 1108966A CN 94117515 A CN94117515 A CN 94117515A CN 94117515 A CN94117515 A CN 94117515A CN 1108966 A CN1108966 A CN 1108966A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The V-Ti coating catalyst of two-segment bed for preparing phenyl anhydride by catalytic oxidation of ortho-xylene or naphthalene on molecular oxygen features that the catalyst for downstream bed includes main active substances of V2O5 and anatase-type TiO2 added with hith-activity TiO2 and analyst promoter of rare-earth elements, rare-earth element mixture, and at least one of the oxides of Sb, P,Zn and Ag, and the catalyst for upstream bed includes the said downstream-bed catalyst plus at least one alkali-metal oxide. The said catalyst has high selectivity and stability.
Description
The present invention relates to a kind of catalyst with ortho-xylene or naphthalene oxidation system phthalic anhydride.More particularly, the present invention relates to ortho-xylene or naphthalene is raw material, the catalyst of catalytic gas phase oxidation system phthalic anhydride in containing the atmosphere of molecular oxygen (abbreviation phthalic anhydride).
As everyone knows, be raw material with ortho-xylene or naphthalene, fixed bed catalytic oxidation system phthalic anhydride, adopting with V and Ti mostly is main active matter, adds Sb, P, Sn, Ag, Nb and alkali metal oxide are at least a to be co-catalyst, the carried catalyst of coated method preparation.
It is carrier with the talcum ring that BASF AG discloses a kind of in DE2546268 number, epimere consists of V-Ti-Rb, hypomere consists of two sections bed catalysts of V-Ti-P, be used for ortho-xylene or naphthalene oxidation system phthalic anhydride, catalyst has good activity and selectivity, disclosing a kind of employing in DE2914638 has the specially-shaped annular carrier of chamfering, at ortho-xylene concentration 84g/NM
3Good selectivity is also arranged.
It is the V-Ti coated catalysts of carrier with the carborundum ring that the Japan public industry of catalyst chemistry company discloses a kind of in JK-76-43732 number, add P, Nb and alkali metal oxide are co-catalyst, are to make the two sections catalyst have suitable performance by the content of adjusting P.The said firm is a co-catalyst for the improvement catalyst has proposed to add Sb in JK86-21729, in JK-89-245857 and JK-90-131141, propose to adopt the special-shaped ring carrier that 4 juts are arranged in the interior or outside of cylindrical ring carrier, can improve catalyst loading, ortho-xylene concentration is at 75g/NM
3, catalyst has selectivity preferably.
Italy Alusuisse company discloses a kind of employing in EP0037492 be the V-Ti-K face coat catalyst of carrier with aluminium oxide or talcum ring, at ortho-xylene concentration 65g/NM
3, 390 ℃ of salt temperatures, having only the low air ratio of employing is air: ortho-xylene=12: in the time of the 1(weight ratio), salt temperature is just reduced to 360 ℃.
Above-mentioned catalyst is because of having preferably active under high load capacity and selectivity is used to industrial production, and the induction period that these catalyst have is long, in use will add SO in unstripped gas
2, the special-shaped ring carrier that will adopt that has just can be applicable to operation under the high load capacity, what have influences product quality because of phthalide content in the raw phthalic anhydride is high, so the performance of catalyst also has improved necessity, particularly also might further improve selection of catalysts.
The object of the present invention is to provide a kind of catalyst that is used for ortho-xylene or naphthalene gas phase catalyst oxidation system phthalic anhydride, make it have good activity, selectivity and stability.
A further object of the present invention provides ortho-xylene or naphthalene catalytic gas phase oxidation system benzene anhydride catalyst, even under high load, also can select to generate highly purified phthalic anhydride.
Another object of the present invention provides the preparation method of benzene anhydride catalyst.
Purpose of the present invention realizes by following technical scheme:
A kind of ortho-xylene and/or naphthalene are raw material and two sections bed V-Ti type coated catalysts that contain molecular oxygen gaseous oxidation system phthalic anhydride, it is characterized in that the oxide of adding rare earth element in the activity of such catalysts component or the mixture of rare earth oxide are co-catalyst.
The invention is characterized in the composition of above-mentioned catalyst and add high-activity titanium deoxide.TiO
2Specific area 3-100m
3/ g, particle diameter is less than 1 μ.
The invention is characterized in when adopting the talcum ring to be carrier Na in the carrier
2O content is less than 0.5%.
Adopt catalyst of the present invention to have following effect:
1. because the present invention has adopted the oxide of rare earth or its mixture as co-catalyst, therefore improved the selectivity of catalyst under high load capacity, when reaction condition is: air speed 3000hr
-1, ortho-xylene concentration 70g/NM
3, 363 ℃ of salt temperatures, phthalic anhydride weight yield 113.0-113.8%, phthalide content is less than 0.04% in the raw phthalic anhydride.
2. because the present invention has added high-activity titanium deoxide in the composition of catalyst, improved the selectivity of catalyst under high load capacity, when reaction condition is air speed 3200hr
-1, 359 ℃ of salt temperatures, ortho-xylene concentration 80g/NM
3, phthalic anhydride weight yield 112.0-113.0%, phthalide content is less than 0.04% in the raw phthalic anhydride.
3. be carrier owing to the present invention adopts the talcum ring of low sodium content, improved the stability of catalyst, prolonged life of catalyst.
Below the present invention is done further detailed description:
The present invention relates to a kind of ortho-xylene or naphthalene and contain the gas of molecular oxygen, two sections bed V-Ti type coated catalysts of gas phase catalyst oxidation system phthalic anhydride, this catalyst is with V
2O
5And TiO
2Be main active material, at least a oxide of Sb, P, Zn, Ag, Mo, Zr, rare earth element and lucium is a co-catalyst, selectively adds alkali-metal at least a oxide as co-catalyst, and it is stated from the inertia heat-resistant carriers.
Catalyst master active material of the present invention is V
2O
5And TiO
2Its gram atom is than being V: Ti=1: 3-80, at least a oxide of Sb, P, Zn, Ag, Mo, Zr, rare earth element and lucium is a co-catalyst, its gram atom ratio to V is 0.001-0.8: 1, wherein preferred Sb, P, Ag, La, Ce, Nd, Pr, preferred especially mixed rare-earth oxide.
In above-mentioned catalyst activity material is formed, add at least a alkali metal oxide again, help further improving selection of catalysts and heat endurance, preferred Li, K, Rb, Cs, the oxide of preferred especially Rb and Cs, alkali metal is 0.001-0.1 to the gram atom ratio of V: 1.
Activity substance content is 1-30Wt% in the catalyst, preferred 5-20Wt%.
Prepare catalyst activity raw material of substance of the present invention and can use oxide, chloride, nitrate, carbonate, phosphate, sulfate, oxalates, acetate, ammonium salt and hydroxide etc.
The used TiO of the present invention
2Can be treated commercially available anatase titanium dioxide TiO
2, also can TiCl
4Be the high activity TiO of raw material with the known method preparation
2Perhaps their mixture, TiO
2Specific surface be 3-100m
2/ g, preferred 5-50m
2/ g, particle diameter be less than 1 μ, preferred 0.01-0.3 μ.
Catalyst of the present invention in preparation be with various salts and oxide dissolution or be suspended in deionized water and organic solvent in, organic solvent can be used ethanol, monoethanolamine, formamide, acetamide and urea etc.
The employed carrier of catalyst of the present invention is that the heat-resisting solid material of employing inertia is a skeleton particle, as the aluminium oxide that dissolves, carborundum, through the magnesium silicate of sintering, alumina silicate, talcum, quartz, pottery etc., synthetic or natural material all can, carrier is with squeezing, press or other known method being shaped to sphere, cylindrical, cylindricality ring, special-shaped ring, preferred cylindricality ring and special-shaped ring.The diameter of carrier is 3-12mm, preferred 5-9mm.Carrier can be atresia or loose structure, and its porosity is 0-60%, Na during preferred 0-50%, particularly carrier form
2The content of O is less than 0.5Wt%, preferably less than 0.3Wt%.Skeleton particle content was greater than 60Wt% during carrier was formed.
Catalyst of the present invention can prepare with known method in the present technique field, for example with the salt and the oxide dissolution of vanadium and various co-catalysts or be suspended in deionized water and organic solvent in, add TiO again
2Preparation active material suspension.Carrier is placed the rotating machinery of coating pan and other type, be heated to 100-400 ℃, preferred 150-300 ℃, with the spraying of active material suspension or be added drop-wise on the carrier, reach 1-30Wt% up to activity substance content, preferred 5-20Wt%.Catalyst in oxidation or reducing atmosphere 400-550 ℃ the activation 2-12 hour.
For making catalyst of the present invention that good selectivity be arranged under high load capacity, adopt two sections bed catalysts in the practice, epimere bed catalyst S is S: X=1: 1-1.4 with the ratio of the bed height of hypomere bed section catalyst X.
Ortho-xylene or naphthalene catalytic gas phase oxidation system phthalic anhydride are to carry out in the fixed bed single tube reactor among the present invention, tube inner diameter is 21-40mm, long 3-4mm, bed height 2.0-3.0mm, reaction tube is made with seamless steel tube for boiler, and reaction tube is provided with sample tap at upper and lower section catalyst intersection and reaction tube exit.The fused salt that the reaction tube external application circulates is a heat carrier, heats or shifts out reaction heat, bed temperature and distribution thermocouple measurement thereof.
The process conditions of oxidation reaction are:
Air speed: 2000-5000hr
-1
Ortho-xylene or naphthalene concentration: 40-85g/NM
3
Salt temperature: 350-380 ℃.
Normally use air as oxygen-containing gas in gaseous mixture, air can be with inert gas dilutions such as nitrogen in case of necessity.
From reaction mixture gas, take out portion of product through sample tap, analyze phthalic anhydride, cis-butenedioic anhydride, unreacted ortho-xylene or naphthalene, the CO in the raw phthalic anhydride in trace impurity phthalide and the tail gas, CO with chromatography and chemical analysis method
2Deng, these all are known methods.
Catalyst of the present invention is used in the industrial installation of producing 5000 tons of phthalic anhydrides per year, has reappeared the single tube result of experiment.
The present invention will be further described below to enumerate embodiment, and unless otherwise indicated all percentages of the present invention are percetage by weight.
Embodiment 1
20 gram vanadic anhydrides are added in 600 milliliters of oxalic acid aqueous solutions that contain 50 gram oxalic acid, heating for dissolving is made the oxalic acid vanadyl solution of avy blue, add 12.18 gram antimony oxides again, 1.26 gram ammonium dihydrogen phosphate (ADP), 0.31 gram cerium oxalate, 0.037 the gram neodymium oxide, 0.51 gram rubidium carbonate, 264 gram specific surface 10m
2The anatase titanium dioxide of/g and 100 gram formamides after stirring, move in the colloid mill to grind and made active material suspension in 1 hour.
With 1000 gram external diameter 8mm, high 6mm, the talcum ring carrier (Na of wall thickness 1.5mm
2O content is less than 0.3Wt%) place the coating pan of diameter 300mm rotation, be preheating to 200-300 ℃, active material suspension is sprayed on the carrier, reaching 10Wt% to activity substance content ends, the catalyst that makes 450 ℃ of activation 6 hours under air atmosphere, its active material is formed gram atom ratio and is:
V∶Ti∶Sb∶P∶Ce∶Nd∶Rb=1∶14∶0.38∶0.05∶0.004∶0.001∶0.02
This catalyst is that the epimere catalyst is hereinafter to be referred as catalyst S.
Lower section catalyst is hereinafter to be referred as catalyst X, and other is formed and the same catalyst S of method for making the rubidium carbonate except that not adding, and its active material gram atom ratio is:
V∶Ti∶Sb∶P∶Ce∶Nd∶Rb＝1∶16∶0.18∶0.15∶0.008∶0.002
For Nd, see Table 1 for catalyst composition and the proportioning that Ce, Pr, Nd prepare with Pr with mixed rare-earth oxide.
Mixed rare-earth oxide represents that with AxOy it consists of:
24-26% La
2O
3, 48-52% CeO
2, 15-17% Nd
2O
3, 5-7% Pr
6O
11, Sm
2O
3And Gd
2O
3, sum is less than 2%.
Table 1 AxOy is with CeO
2Meter
The catalyst catalyst is formed the gram atom ratio
S-1-2 V:Ti:Sb:P:Ce:Pr:Rb=1:14:0.38:0.05:0.004:0.001:0.02
X-1-2 V:Ti:Sb:P:Ce:Pr=1:16:0.18:0.15:0.008:0.002
S-1-3 V:Ti:Sb:P:A:Rb=1:14:0.38:0.05:0.005:0.02
X-1-3 V:Ti:Sb:P:A=1:16:0.18:0.15:0.01
S-1-4 V:Ti:Sb:P:A:Rb=1:14:0.38:0.05:0.01:0.02
X-1-4 V:Ti:Sb:P:A=1:16:0.18:0.15:0.02
25 millimeters of internal diameters, about 1.2 liters of above-mentioned S-X catalyst of packing in long 4 meters the boiler steel single tube reactor, 1.2 meters of epimere bed heights, 1.6 meters of hypomere bed heights, reaction tube is with the heating of the fuse salt of flow circuit or shift out heat, distributes with the thermocouple measurement bed temperature.
The analysis gas chromatographic analysis of trace impurity phthalide in ortho-xylene purity, conversion ratio, the raw phthalic anhydride in the experiment, product phthalic anhydride and byproduct cis-butenedioic anhydride are analyzed with chemical method.
Except that specifying, ortho-xylene conversion ratio 100%, phthalide content is as follows less than 0.04Wt%(in the raw phthalic anhydride in the example).
The test process conditions and the results are shown in Table 2:
React the cumulative time in the following example if no special instructions with example 1.
Adopt the catalyst of table 1 as known from Table 2, react ortho-xylene concentration on the 30th and can bring up to 70g/NM
3, phthalic anhydride weight yield 113.0-113.8% illustrates this catalyst selectivity height, induction period is short.
Embodiment 2
Remove catalyst (S, X) AxOy is respectively 0.019 gram and 0.038 gram in the active material, outside adding behind molten Jies of acid, other is with routine 1-3.
At air speed 3200hr
-1, ortho-xylene concentration 60g/NM
3, 367 ℃ of salt temperatures, phthalic anhydride weight yield 113.7%.
Fig. 2
Catalyst accumulative total reaction velocity ortho-xylene salt temperature phthalic anhydride yield yield of maleic anhydride
Every other day hr during numbering
-1Concentration g/NM
3℃ Wt% Wt%
S-X-1-1 10 3000 40 378 113.9 5.2
20 3000 60 368 113.2 5.4
30 3000 70 364 113.0 5.8
S-X-1-2 10 3000 40 378 114.0 5.0
20 3000 60 368 113.3 5.3
30 3000 70 363 113.6 5.6
S-X-1-3 20 3000 60 367 113.8 5.1
30 3000 70 362 113.8 5.5
S-X-1-4 20 3100 60 367 113.6 5.0
30 3100 70 362 113.4 5.3
Embodiment 3
Remove with 0.86 gram nitric acid
Replace outside the rubidium carbonate, other is with routine 1-3, at air speed 3200hr
-1, ortho-xylene concentration 60g/NM
3, 369 ℃ of salt temperatures, phthalic anhydride weight yield 113.3%.
Embodiment 4
Remove in routine 1-3 catalyst is formed and add an amount of silver nitrate or zinc nitrate again, or replace outside the P with Ag or Zn, other is with routine 1-3, the process conditions of test and the results are shown in Table 3.
Table 3 air speed 3000hr
-1, ortho-xylene concentration 60g/NM
3
Catalyst salt bath phthalic anhydride
The temperature yield
Numbering is formed and proportioning ℃ Wt%
S-4-1 V:Ag=1:0.05 add Ag other with example 1-3 367 113.7
X-4-1 V:Ag=1:0.05 add Ag other with example 1-3
S-4-2 V:Zn=1:0.05 add Zn other with example 1-3 367 113.5
X-4-2 V:Zn=1:0.05 add Zn other with example 1-3
S-4-3 V:Ag=1:0.05 divided by Ag for P outer other with routine 1-3 370 113.0
X-4-3 V:Ag=1:0.05 divided by Ag for P outer other with routine 1-3
S-4-4 V:Zn=1:0.05 divided by Zn for P outer other with routine 1-3 370 112.2
X-4-4 V:Zn=1:0.15 divided by Zn for P outer other with routine 1-3
Embodiment 5
Replace Sb divided by antimony oxalate or vanadic acid antimony
2O
3, other is with example 1-4 outward, experimental condition and the results are shown in Table 4.
Table 4 air speed 3000hr
-1
Catalyst contains antimony material accumulative total and reacts ortho-xylene salt temperature phthalic anhydride yield
Every other day concentration g/NM during numbering
3℃ Wt%
5-1 vanadic acid antimony 15 60 367 113.7
25 70 363 113.6
5-2 antimony oxalate 15 60 367 113.2
25 70 363 113.5
Replace Sb with vanadic acid antimony or antimony oxalate as shown in Table 4
2O
3Can further reduce the induction period of catalyst.
Embodiment 6
Other is with routine 1-3 except that the Sb content that changes catalyst S.The test process conditions and the results are shown in Table 5.
Table 5 air speed 3000hr
-1
The neighbour xylene concentration salt temperature ℃ phthalic anhydride yield Wt% of catalyst numbering V:Sb gram atom
g/NM
3
S-6-1 1:0.18 60 367 113.6
S-6-2 1:0.58 60 368 113.9
S-6-3 1:0.78 60 370 112.7
Embodiment 7
Add a certain amount of active titanic dioxide in catalyst is formed, suitably adjust the content of co-catalyst Rb simultaneously, other is with routine 1-3, experimental condition and the results are shown in Table 6.
Table 6 air speed 3200hr
-1
The dense salt temperature phthalic anhydride of catalyst activity titanium dioxide V:Rb ortho-xylene yield
Total amount
The numbering titanium is with TiO
2Meter % gram atom is than degree g/NM
3℃ Wt%
S-7-1 5 1:0.02 60 368 113.1
X-7-1 5 70 363 113.6
80 359 113.0
S-7-2 10 1:0.028 60 366 113.5
X-7-2 5 70 362 113.2
80 358 112.8
S-7-3 15 1:0.038 60 366 113.2
X-7-3 5 70 361 112.8
80 358 112.0
As can be known from the results of Table 6, add an amount of active titanic dioxide, can improve activity and the selectivity of catalyst under high load capacity.
Embodiment 8
Except that using carborundum ring and Alpha-alumina ring to replace the talcum ring, other is with routine 1-3.Experimental condition and the results are shown in Table 7.
Table 7 air speed 3000hr
-1Ortho-xylene concentration 60g/NM
3
The kind of carrier transitivity
The salt bath phthalic anhydride
Kind skeleton particle particle diameter porosity temperature yield
% ℃ of Wt% of content Wt% mm
Carborundum ring SiC〉85 φ 8x6x1.5 30-40 367 113.5
A-aluminium oxide ring a-Al
2O
385 φ 8x6x1.5 30-40 367 113.2
Embodiment 9
The catalyst of example 1-3 enlarges preparation through 20 kilograms every batch.Reactor diameter 2400mm, high 5040mm, in 3306 internal diameter 25mm are arranged, long 3226mm boiler steel reaction tube, pipe inner catalyst X filling 1.6m, catalyst S filling 1.2m, other is equipped with and surveys bed temperature and survey respectively 5 of salt temperature pipes.
At air speed 3000hr
-1, ortho-xylene concentration 60g/nm
3, under the reaction condition that salt temperature is 360 ℃, reactor outlet sampling ortho-xylene conversion ratio 100%, phthalic anhydride weight yield 113%, phthalide content is less than 0.03% in the raw phthalic anhydride.
Comparative example 1
Catalyst activity material gram atom ratio is:
V: Ti: Sb: Ce=1: catalyst loaded 1.0 liters in 14: 0.38: 0.02, height of bed 2.2m, and the evaluation experimental that carries out catalyst with the device of embodiment 1 the results are shown in Table 8:
The oxide that adds Sb and Ce as known from Table 3 in V-Ti forms is a co-catalyst, though catalyst activity, selectivity is all good, does not add Rb, does not adopt two sections beds, and ortho-xylene concentration is greater than 55g/NM
3The time hot(test)-spot temperature control unstable, so this catalyst is suitable for application under the high load capacity.
Table 8
Air speed ortho-xylene reaction temperature ℃ phthalic anhydride cis-butenedioic anhydride
Hr
-1Concentration yield yield
G/NM
3Bathe warm spot Wt% Wt%
3200 40 370 460 112.2 3.6
3200 50 365 470 111.8 3.9
3200 55 363 480 112.1 3.6
Comparative example 2
Except that not adding the rare-earth oxidation beyond the region of objective existence in the catalyst composition, other is with routine 1-3, at air speed 3000hr
-1, ortho-xylene concentration 60g/NM
3370 ℃ of salt temperatures, phthalic anhydride weight yield 111.8%, cis-butenedioic anhydride weight yield 7.2%Wt%, phthalide content is 0.07% in the raw phthalic anhydride.
Comparative example 3
Remove Preparation of Catalyst form with talcum ring carrier in Na
2O content is outer other the same 1-3 of 0.98Wt%, and it is tested process conditions and the results are shown in Table 9.
As known from Table 9, because of catalyst reaction at high temperature for a long time, the sodium in the carrier migrates in the active material, and catalyst selectivity is descended, and the phthalic anhydride yield reduces.
Na in the active material of table 9 catalyst activation back
2O content is 0.024Wt%.
Reaction accumulative total catalyst activity thing air speed ortho-xylene concentration salt temperature phthalic anhydride yield
The time every other day matter in Na
2OWt% hr
-1G/NM
3℃ Wt%
10 3000 40 378 113.6
20 3000 60 367 113.4
180 0.26 3000 60 368 111.2
Claims (8)
1, a kind of is raw material and two sections bed V-Ti type coated catalysts that contain molecular oxygen catalytic gas phase oxidation system phthalic anhydride with ortho-xylene or naphthalene, it is characterized in that the hypomere bed catalyst is with V
2O
5And TiO
2Be main active material, its gram atom is than being V: Ti=1: 3-80, and co-catalyst is the oxide of the mixture that is selected from least a rare earth element, rare earth element, Sb, P, Zn, Ag, Mo, Zr, its to gram atom of V than being 0.001-0.8: 1; The catalyst activity material is stated from the inorganic carrier, the catalyst activity content of material 1-30Wt% that makes, the epimere bed catalyst is that to add at least a alkali metal oxide again in activity is formed be co-catalyst, its to gram atom of V than being 0.001-0.1: 1, other same lower section catalyst.
2,, it is characterized in that described rare earth oxide comprises CeO according to the catalyst of claim 1
2, Nd
2O
3, Pr
6O
11
3,, it is characterized in that the mixture of described rare earth oxide consists of: La according to the catalyst of claim 1
2O
324-26%, CeO
248-52%, Nd
2O
315-17%, Pr
6O
115-7%, Sm
2O
3And Gd
2O
3Sum is less than 2%.
4,, it is characterized in that described alkali metal oxide comprises the oxide of Rb or Cs according to the catalyst of claim 1.
5,, it is characterized in that described Sb comprises antimony oxide, vanadic acid antimony or antimony oxalate according to the catalyst of claim 1.
6, according to the catalyst of claim 1, it is characterized in that described inorganic carrier is to be selected from a kind of in the carborundum of talcum, fusion and the aluminium oxide, it is shaped as annular, cylindrical, spherical, and diameter is 3-12mm, porosity 0-60%.
7, according to the catalyst of claim 6, when adopting the talcum ring to be carrier, Na in the carrier
2O content is less than 0.5%.
8,, it is characterized in that described TiO according to the catalyst of claim 1
2Be anatase titanium dioxide TiO
2With high activity TiO
2Or their mixture, TiO
2Specific area 3-100m
2/ g, particle diameter is less than 1 μ.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU245032A1 (en) * | 1967-06-30 | 1984-05-15 | Lyubarskij A G | Method for preparing catalyst for producing phthalic anhydride |
| SU630255A1 (en) * | 1976-07-12 | 1978-10-30 | Ордена Трудового Красного Знамени институт химических наук Казахской ССР | Method of obtaining 4-tret-butylphthalic acid anhydride |
| JPS5857416B2 (en) * | 1977-11-09 | 1983-12-20 | 三井東圧化学株式会社 | Novel method for producing anthraquinone |
| RU2035219C1 (en) * | 1992-04-10 | 1995-05-20 | Институт катализа СО РАН | Catalyst for oxidizing o-xylene into phthalic anhydride; technique |
| US6591618B1 (en) * | 2002-08-12 | 2003-07-15 | Praxair Technology, Inc. | Supercritical refrigeration system |
-
1994
- 1994-10-25 CN CN94117515A patent/CN1047959C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059131C (en) * | 1997-10-29 | 2000-12-06 | 天津市西青区杨柳青镇工艺印刷厂 | Catalyst for producing benzoic anhydride |
| EP0945180A3 (en) * | 1998-03-17 | 2000-06-14 | Nippon Shokubai Co., Ltd. | Catalyst and production process for pyromellitic dianhydride |
| CN1113883C (en) * | 1998-03-17 | 2003-07-09 | 株式会社日本触媒 | Production process for pyromellitic dianhydride |
| CN100496740C (en) * | 2004-05-29 | 2009-06-10 | 苏德-化学股份公司 | Multi-layer catalyst for producing phthalic anhydride |
| CN102658188A (en) * | 2012-05-11 | 2012-09-12 | 石家庄昊普化工有限公司 | Double-layer catalyst and preparation thereof, and application of catalyst in preparation of pyromellitic dianhydride |
| CN106215690A (en) * | 2016-07-28 | 2016-12-14 | 叶君芝 | A kind of composite promoting Degradation Formaldehyde and preparation method thereof |
| CN110871098A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride from naphthalene and preparation method and application thereof |
| CN112547103A (en) * | 2019-09-26 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride by oxidation 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 |
| CN110711575A (en) * | 2019-10-22 | 2020-01-21 | 黄骅市信诺立兴精细化工股份有限公司 | Catalyst for preparing 1, 8-naphthalic anhydride and preparation method thereof |
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| Publication number | Publication date |
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| CN1047959C (en) | 2000-01-05 |
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