CN110560036A - Catalyst for preparing 1, 8-naphthalic anhydride and preparation method thereof - Google Patents
Catalyst for preparing 1, 8-naphthalic anhydride and preparation method thereof Download PDFInfo
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- CN110560036A CN110560036A CN201910715528.XA CN201910715528A CN110560036A CN 110560036 A CN110560036 A CN 110560036A CN 201910715528 A CN201910715528 A CN 201910715528A CN 110560036 A CN110560036 A CN 110560036A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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Abstract
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing 1, 8-naphthalic anhydride and a preparation method thereof, which have the advantages of high activity, high catalytic efficiency and high reaction efficiency; the catalyst comprises a carrier, a catalytic active substance and a cocatalyst, wherein the catalytic active substance covers the carrier and contains vanadium pentoxide and titanium dioxide, wherein the mass content of the vanadium pentoxide is 2-25% of the total mass of the catalytic active substance, and the cocatalyst is one or a combination of alkali metals, Sb, P, Nb and La; the preparation method comprises the following steps: (1) preparation of suspension a: dissolving 40-120 g of vanadium salt, 10-50 g of auxiliary agent salt and 10-100 g of oxalic acid in water, adding 10-300 g of binder and 120-1000 g of titanium dioxide, and uniformly mixing and emulsifying; (2) preparing a catalyst: and spraying the suspension A to the surface of 1-10L of pumice with the diameter of 2-12 mm by using a spray gun, drying, and roasting to obtain the vanadium-titanium 1, 8-naphthalic anhydride catalyst.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for preparing 1, 8-naphthalic anhydride and a preparation method thereof.
background
1, 8-naphthalic anhydride is an important chemical raw material, can be used for manufacturing organic dyes, pigments and pesticides, can also generate 2, 6-naphthalenedicarboxylic acid after transposition, and further produces high-end resin such as polyethylene naphthalate (PEN), and has high market value.
At present, most of catalysts for preparing 1, 8-naphthalic anhydride by using acenaphthene air oxidation method are traditional pumice-loaded V-Sn and V-K catalysts which are low in activity and can only be used at low space velocity (1300-1600/h) and low acenaphthene concentration (20 g/m)3) The following reaction results in a low reaction efficiency, and the mass yield of 1, 8-naphthalic anhydride is only about 70%.
Chinese patent 101601996 discloses a three-stage bed catalyst combination for preparing 1, 8-naphthalic anhydride, which comprises vanadium-potassium catalyst, vanadium-tin catalyst and vanadium-lithium catalyst, and has high yield of 1, 8-naphthalic anhydride, but low catalyst efficiency and low yield of 1, 8-naphthalic anhydride per unit volume of catalyst.
Disclosure of Invention
In order to solve the above technical problems, it is an object of the present invention to provide a catalyst for preparing 1, 8-naphthalic anhydride, which has high activity, high catalytic efficiency, and high reaction efficiency;
it is another object of the present invention to provide a method for preparing a catalyst for use in the preparation of 1, 8-naphthalic anhydride.
The catalyst for preparing 1, 8-naphthalic anhydride comprises a carrier, a catalytic active substance and a cocatalyst, wherein the catalytic active substance covers the carrier, the catalytic active substance contains vanadium pentoxide and titanium dioxide, the mass content of the vanadium pentoxide accounts for 2% -25% of the total mass of the catalytic active substance, the cocatalyst is one or a combination of more of alkali metals, Sb, P, Nb and La, and the alkali metals are one or more of lithium, sodium, potassium, rubidium and cesium.
The catalyst for preparing 1, 8-naphthalic anhydride of the invention has pumice as the carrier.
The catalyst for preparing 1, 8-naphthalic anhydride of the invention has the addition amount of the catalytic active substance accounting for 2-25% of the total mass of the catalyst.
The catalyst for preparing 1, 8-naphthalic anhydride of the invention has the following molar ratio of the total addition amount of the cocatalyst to vanadium atoms: (0.01:1) to (0.5: 1).
The preparation method of the catalyst for preparing 1, 8-naphthalic anhydride comprises the following steps:
(1) Preparation of suspension a: dissolving 40-120 g of vanadium salt, 10-50 g of auxiliary agent salt and 10-100 g of oxalic acid in water, adding 10-300 g of binder, adding 120-1000 g of titanium dioxide, uniformly mixing and emulsifying to obtain a suspension A;
(2) Preparing a catalyst: and spraying the suspension A to the surface of 600-1800 mL pumice with the diameter of 2-12 mm by using a spray gun, drying, and roasting to obtain the vanadium-titanium 1, 8-naphthalic anhydride catalyst.
According to the preparation method of the catalyst for preparing 1, 8-naphthalic anhydride, the vanadium salt used in the step (1) is ammonium vanadate, vanadyl oxalate or other soluble vanadium salt.
In the method for preparing a catalyst for preparing 1, 8-naphthalic anhydride according to the present invention, the titanium dioxide used in the step (1) is anatase type titanium dioxide.
According to the preparation method of the catalyst for preparing 1, 8-naphthalic anhydride, the binder used in the step (1) is one or more of vinyl acetate, polyethylene glycol, polyvinyl alcohol, acrylate and vinyl laurate.
According to the preparation method of the catalyst for preparing 1, 8-naphthalic anhydride, the drying treatment temperature in the step (2) is 30-150 ℃, and the drying time is 2-48 h.
According to the preparation method of the catalyst for preparing 1, 8-naphthalic anhydride, the roasting temperature in the step (2) is 300-650 ℃, and the roasting time is 2-24 hours.
Compared with the prior art, the invention has the beneficial effects that: the catalyst for preparing 1, 8-naphthalic anhydride has the advantages of good reaction selectivity, easy preparation, good repeatability and stable performance when the 1, 8-naphthalic anhydride is prepared, and can improve the quality yield of the 1, 8-naphthalic anhydride in the preparation process of the 1, 8-naphthalic anhydride.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
60g of ammonium metavanadate, 10g of potassium sulfate and 90g of oxalic acid are dissolved in water, 30g of acrylic ester is added to prepare a solution, 200g of anatase titanium dioxide is added, after uniform emulsification, a suspension is sprayed onto 600ml of pumice by a spray gun, drying is carried out at the temperature of 110 ℃, and baking is carried out for 4 hours at the temperature of 400 ℃ to obtain the 1, 8-naphthalic anhydride catalyst 1.
the oxidation reaction of synthesizing 1, 8-naphthalic anhydride by oxidizing acenaphthene with air is carried out in a stainless steel tubular reactor, the length of the reactor is 3.5m, the inner diameter is 25mm, the reactor is heated and insulated by molten salt, the filling amount of the catalyst is 850ml, the air for oxidation can be provided by an air compressor, the air is preheated, mixed and gasified with acenaphthene, and then enters a catalyst bed layer to start the oxidation reaction, the oxidation product passes through a thin-wall condenser, all organic reaction products are collected, weighed and analyzed.
Example 2
60g of ammonium metavanadate, 10g of potassium sulfate, 90g of oxalic acid and 60g of lanthanum nitrate are dissolved in water, 30g of acrylic ester is added to prepare a solution, 200g of anatase titanium dioxide is added, after uniform emulsification, a suspension is sprayed onto 600ml of pumice by a spray gun, drying is carried out at 110 ℃, and baking is carried out at 400 ℃ for 4 hours to obtain the 1, 8-naphthalic anhydride catalyst 2.
the oxidation reaction of synthesizing 1, 8-naphthalic anhydride by oxidizing acenaphthene with air is carried out in a stainless steel tubular reactor, the length of the reactor is 3.5m, the inner diameter is 25mm, the reactor is heated and insulated by molten salt, the filling amount of the catalyst is 850ml, the air for oxidation can be provided by an air compressor, the air is preheated, mixed and gasified with acenaphthene, and then enters a catalyst bed layer to start the oxidation reaction, the oxidation product passes through a thin-wall condenser, all organic reaction products are collected, weighed and analyzed.
Example 3
48g of ammonium metavanadate, 8g of potassium sulfate and 50g of oxalic acid are dissolved in water, 20g of acrylic ester is added to prepare a solution, 200g of anatase titanium dioxide is added, after uniform emulsification, a suspension is sprayed onto 600ml of pumice by a spray gun, drying is carried out at the temperature of 110 ℃, and baking is carried out for 4 hours at the temperature of 400 ℃ to obtain the 1, 8-naphthalic anhydride catalyst 3.
The oxidation reaction of synthesizing 1, 8-naphthalic anhydride by oxidizing acenaphthene with air is carried out in a stainless steel tubular reactor, the length of the reactor is 3.5m, the inner diameter is 25mm, the reactor is heated and insulated by molten salt, the filling amount of the catalyst is 850ml, the air for oxidation can be provided by an air compressor, the air is preheated, mixed and gasified with acenaphthene, and then enters a catalyst bed layer to start the oxidation reaction, the oxidation product passes through a thin-wall condenser, all organic reaction products are collected, weighed and analyzed.
Example 4
Dissolving 10g of ammonium metavanadate, 1g of cesium sulfate and 10g of oxalic acid in water, adding 15g of formamide to prepare a solution, adding 200g of anatase titanium dioxide, uniformly emulsifying, spraying the suspension onto 600ml of pumice by using a spray gun, drying at 110 ℃, and baking at 400 ℃ for 4 hours to obtain the 1, 8-naphthalic anhydride catalyst 4.
The oxidation reaction of acenaphthene air oxidation synthesis 1, 8-naphthalic anhydride is carried out in a stainless steel tubular reactor, the length of the reactor is 3.5m, the inner diameter is 25mm, the reactor is heated and insulated by fused salt, and the filling amount of the catalyst is 850 ml. Air for oxidation can be provided by an air compressor, the air is preheated and then mixed with acenaphthene for gasification, the air enters a catalyst bed layer to start oxidation reaction, and the oxidation product passes through a thin-wall condenser, and all organic reaction products are collected, weighed and analyzed.
Under the reaction conditions: the temperature of the molten salt is 340 ℃, and the space velocity is 3.0Nm3catalyst/L, acenaphthene concentration 40g/Nm3The catalysts obtained in examples 1 to 4 above were evaluated for the catalytic performance of 1, 8-naphthalic anhydride by the air oxidation of acenaphthylene under air to obtain the following results:
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The catalyst for preparing 1, 8-naphthalic anhydride is characterized by comprising a carrier, a catalytic active substance and a cocatalyst, wherein the catalytic active substance covers the carrier and contains vanadium pentoxide and titanium dioxide, the mass content of the vanadium pentoxide accounts for 2% -25% of the total mass of the catalytic active substance, the cocatalyst is one or a combination of more of alkali metals, Sb, P, Nb and La, and the alkali metals are one or more of lithium, sodium, potassium, rubidium and cesium.
2. the catalyst for the preparation of 1, 8-naphthalic anhydride according to claim 1, wherein the support is pumice.
3. The catalyst for preparing 1, 8-naphthalic anhydride according to claim 1, wherein the amount of the catalytically active material added is 2 to 25% of the total mass of the catalyst.
4. The catalyst for the preparation of 1, 8-naphthalic anhydride of claim 1 wherein the total amount of promoter added is in a molar ratio to vanadium atoms of: (0.01:1) to (0.5: 1).
5. A method for preparing a catalyst for use in the preparation of 1, 8-naphthalic anhydride, comprising the steps of:
(1) Preparation of suspension a: dissolving 40-120 g of vanadium salt, 10-50 g of auxiliary agent salt and 10-100 g of oxalic acid in water, adding 10-300 g of binder, adding 120-1000 g of titanium dioxide, uniformly mixing and emulsifying to obtain a suspension A;
(2) Preparing a catalyst: and spraying the suspension A to the surface of 600-1800 mL pumice with the diameter of 2-12 mm by using a spray gun, drying, and roasting to obtain the vanadium-titanium 1, 8-naphthalic anhydride catalyst.
6. The method for preparing a catalyst for use in the preparation of 1, 8-naphthalic anhydride according to claim 5, wherein the vanadium salt used in the step (1) is ammonium vanadate, vanadyl oxalate or other soluble vanadium salt.
7. The method for producing a catalyst for use in producing 1, 8-naphthalic anhydride according to claim 5, wherein the titanium dioxide used in the step (1) is anatase titanium dioxide.
8. the method for preparing a catalyst for 1, 8-naphthalic anhydride according to claim 5, wherein the binder used in the step (1) is one or more of vinyl acetate, polyethylene glycol, polyvinyl alcohol, acrylate, and vinyl laurate.
9. The method for preparing a catalyst for 1, 8-naphthalic anhydride according to claim 5, wherein the temperature of the drying treatment in the step (2) is 30 to 150 ℃ and the drying time is 2 to 48 hours.
10. The method for preparing a catalyst for 1, 8-naphthalic anhydride according to claim 5, wherein the calcination temperature in the step (2) is 300 ℃ to 650 ℃ and the calcination time is 2 to 24 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030571A (en) * | 1987-04-10 | 1989-01-25 | 新日铁化学株式会社 | The preparation method of Tetra hydro 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 |
| CN101422727A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Benzoic anhydride catalyst and preparation method thereof |
| CN101443304A (en) * | 2006-05-23 | 2009-05-27 | 苏德-化学股份公司 | Use of, and method using a catalyst containing titanium dioxide, particularly for the production of phthalic anhydride |
| CN101601996A (en) * | 2009-07-03 | 2009-12-16 | 辽宁联港染料化工有限公司 | Preparation 1, the catalyst of 8-naphthalene acid anhydride |
-
2019
- 2019-08-05 CN CN201910715528.XA patent/CN110560036A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030571A (en) * | 1987-04-10 | 1989-01-25 | 新日铁化学株式会社 | The preparation method of Tetra hydro 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 |
| CN101443304A (en) * | 2006-05-23 | 2009-05-27 | 苏德-化学股份公司 | Use of, and method using a catalyst containing titanium dioxide, particularly for the production of phthalic anhydride |
| CN101422727A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Benzoic anhydride catalyst and preparation method thereof |
| CN101601996A (en) * | 2009-07-03 | 2009-12-16 | 辽宁联港染料化工有限公司 | Preparation 1, the catalyst of 8-naphthalene acid anhydride |
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Application publication date: 20191213 |