CN1332143A - Gaseous oxidation and liquid-solid extraction process in a low-temperature short fluidized bed to prepare 1,4-naphthaquinone - Google Patents
Gaseous oxidation and liquid-solid extraction process in a low-temperature short fluidized bed to prepare 1,4-naphthaquinone Download PDFInfo
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- CN1332143A CN1332143A CN 01127954 CN01127954A CN1332143A CN 1332143 A CN1332143 A CN 1332143A CN 01127954 CN01127954 CN 01127954 CN 01127954 A CN01127954 A CN 01127954A CN 1332143 A CN1332143 A CN 1332143A
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- naphthalene
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Abstract
It the 1,4-naphthaquinone preparing process a catalyst comprising V2O52-7%.K2O3-10%, nSiO2.xH2O 50-90 %, SO3 2-12%, P2O5 0.1-10 %, SnO2 0.1-8 % and Fe2O3 1-10% is used. Owing to short reaction bed, lower reaction temp. and concentrated six-element components, the present invention has less solvent consumption, less water consumption, less investment in equipment, naphthalene converting rate as high as 82-99 %, and lower naphthalene content in raw naphthaquinone product and thus high application value.
Description
Gu a kind of method of utilizing low temperature dwarf forms fluidized-bed oxidation and liquid-leaching preparation 1.4 naphthoquinones.
At present, the preparation of 1.4 naphthoquinones mainly contains liquid-phase oxidation and two kinds of methods of gaseous oxidation.In liquid-phase oxidation, can be divided into chemical method and electrooxidation method again.Because what the oxygenant in the liquid chemical method was used is chromic salt, but produce a large amount of carcinogenic waste water, Gu Er, though reaction temperature and, yield is higher, but only is applicable to that the laboratory prepares on a small quantity; Though liquid phase electrooxidation method reaction temperature and, the yield height because current consumption is too big, also only is in lab scale or pilot scale level.Reach the suitability for industrialized production level so have only gaseous oxidation to prepare 1.4 naphthoquinones at present.
Gaseous oxidation is divided into two kinds of fixed bed and fluidized-beds again.In the preparation of fixed bed catalyst, with support material such as silica gel or diatomite, siliceous atlapulgite, silicon sol, vitriolate of tartar, potassium pyrosulfate, Vanadium Pentoxide in FLAKES, active constituent mixing moulding, calcination prepares.
In order to improve activity and selectivity, can reach by the distribute control of pore volume and add of carrier aperture to the control of carrier, diatomaceous cleanup acid treatment and catalyst structure and when adding new cocatalyst component and iron, tungsten and iron and tin.Can also improve by the filling method that adds a certain amount of sulfurous gas and control catalyst.
Utilize the above-mentioned method that goes up, can make the yield of fixed bed legal system 1.4 naphthoquinones reach 40mol%-42mol%, pay the product phthalic anhydride simultaneously.
Compare with fixed bed, fluidized-bed has less investment, equipment is simple, temperature of reaction is easy to control and because the dissemination of catalyst particle makes that the operation high density becomes possibility in limits of explosion.But, make fluidized-bed possess certain degree of difficulty with the exploitation of catalyzer because fluidized-bed possesses to the requirement of the wear-resisting intensity of catalyzer and high reactivity, high conversion, highly selective the time.The highest naphthalene transformation efficiency also has only 82%, naphthoquinones yield 38mol%, and also reaction must be at diameter 40mm, carries out under the high temperature of the higher fluidized-bed of high 1000mm and 400 ℃.
Gu the objective of the invention is will be by the method for a kind of hexa-atomic prescription and shorter fluidized-bed oxidation and liquid-leaching, prepare 1.4 naphthoquinones at a lower temperature, make its than before method, have few with quantity of solvent, the water yield is few, naphthoquinones yield height, naphthalene transformation efficiency height, the few and characteristic of simple of facility investment.
The catalyst formulation that the present invention uses is as follows:
V
2O
5(Vanadium Pentoxide in FLAKES) 2-7%
k
2O (potassium oxide) 3-10%
NSiO
2.XH
2O (silica gel) 50-90%
SO
3(sulphur trioxide) 2-12%
P
2O
5(Vanadium Pentoxide in FLAKES) 0.1-10%
SnO
2(tindioxide) 0.1-8%
Fe
2O
3(ferric oxide) 1-10%
The present invention is 100% by the sum total of each component of catalyzer that this formulation forms, and preparation process is as follows:
With solid industrial naphthalene or refined naphthalene, put into vaporizer (or molten naphthalene groove) and be heated to 80 ℃-130 ℃, 15-40: 1 air naphthalene is than adding air, bring the fluidized-bed that contains with the microspheric catalyst of above-mentioned formulation into the mixture that air compressor machine or gas blower will be vaporized or liquefy, under 270 ℃-380 ℃ temperature, react, condensation in 5 ℃ of-25 ℃ of normal temperature airs, draw the solid mixture of phthalic anhydride and naphthoquinones, again solid mixture with dimethylbenzene or 65 ℃ of-135 ℃ of boiling point aliphatic hydrocarbons, be heated to boiling extraction, 60 ℃ of-80 ℃ of condensations again, separate out phthalic anhydride, centrifugation then.After leaching liquid repeatedly leached or concentrating, condensation is reduced between 5 ℃-25 ℃.Filter or centrifugation, tell the solvent recuperation utilization, separate out the crude product naphthoquinones, this crude product naphthoquinones is dissolved in the dimethylbenzene or aliphatic hydrocarbon of the water that contains 5-30% and 95-70%, be heated to boiling, cool the temperature to 70 ℃-90 ℃ after, tell the water layer that contains phthalic acid with skimmer, oil reservoir is cooled to 5 ℃-25 ℃, and the elaboration naphthoquinones is separated out in condensation.
The fluidized-bed diameter that the present invention uses is 38mm-42mm, highly is 500mm-650mm.As the micro-spherical silica gel of carrier, its diameter is 70-110 μ.
The present invention is owing to adopt shorter reaction bed, lower temperature of reaction and dense hexa-atomic component, it is had under the undiminished prerequisite of naphthoquinones yield, solvent load is few, water consumption reaches facility investment less and reaches naphthalene transformation efficiency 82-99% less and make that naphthalene content is extremely low in the crude product naphthoquinones, the characteristics that are easy to purify have great using value.
The present invention will be further described now to lift an example.
Embodiment: catalyst formulation is as follows:
V
2O
5(Vanadium Pentoxide in FLAKES) 3%
k
2O (potassium oxide) 5%
NSiO
2.XH
2O (silica gel) 64%
SO
3(sulphur trioxide) 10%
P
2O
5(Vanadium Pentoxide in FLAKES) 5%
SnO
2(tindioxide) 6%
Fe
2O
3(ferric oxide) 7%
The sum total of each component of catalyzer that the present invention forms by this formulation is that 100% preparation process is as follows:
With solid industrial naphthalene or refined naphthalene, put into vaporizer (or molten naphthalene groove) and be heated to 90 ℃, 30: 1 air naphthalene is than adding air, bring the fluidized-bed that contains with the microspheric catalyst of above-mentioned formulation into the mixture that air compressor machine or gas blower will be vaporized or liquefy, under 300 ℃ temperature, react, condensation in 20 ℃ of normal temperature airs, draw the solid mixture of phthalic anhydride and naphthoquinones, again solid mixture with dimethylbenzene or 100 ℃ of boiling point aliphatic hydrocarbons, be heated to boiling extraction, 70 ℃ of condensations again, separate out phthalic anhydride, centrifugation then.After leaching liquid repeatedly leached or concentrating, condensation is reduced between 20 ℃, filter or centrifugation, tell the solvent recuperation utilization, separate out the crude product naphthoquinones, this crude product naphthoquinones is dissolved in the dimethylbenzene or aliphatic hydrocarbon that contains 20% water and 90%, be heated to boiling, cool the temperature to 80 ℃ after, tell the water layer that contains phthalic acid with skimmer, oil reservoir is cooled to 20 ℃, and the elaboration naphthoquinones is separated out in condensation.
Claims (1)
- Gu a kind of method of utilizing low temperature dwarf forms fluidized-bed oxidation and liquid-leaching preparation 1.4 naphthoquinones, it is characterized in that: catalyst formulation is as follows:V 2O 5(Vanadium Pentoxide in FLAKES) 2-7%k 2O (potassium oxide) 3-10%NSiO 2.XH 2O (silica gel) 50-90%SO 3(sulphur trioxide) 2-12%P 2O 5(Vanadium Pentoxide in FLAKES) 0.1-10%SnO 2(tindioxide) 0.1-8%Fe 2O 3(ferric oxide) 1-10%The present invention is 100% by the sum total of each component of catalyzer that this formulation forms, and preparation process is as follows:With solid industrial naphthalene or refined naphthalene, put into vaporizer (or molten naphthalene groove) and be heated to 80 ℃-130 ℃, 15-40: 1 air naphthalene is than adding air, bring the fluidized-bed that contains with the microspheric catalyst of above-mentioned formulation into the mixture that air compressor machine or gas blower will be vaporized or liquefy, under 270 ℃-380 ℃ temperature, react, condensation in 5 ℃ of-25 ℃ of normal temperature airs, draw the solid mixture of phthalic anhydride and naphthoquinones, again solid mixture with dimethylbenzene or 65 ℃ of-135 ℃ of boiling point aliphatic hydrocarbons, be heated to boiling extraction, 60 ℃ of-80 ℃ of condensations again, separate out phthalic anhydride, centrifugation then.After leaching liquid repeatedly leached or concentrating, condensation is reduced between 5 ℃-25 ℃.Filter or centrifugation, tell the solvent recuperation utilization, separate out the crude product naphthoquinones, this crude product naphthoquinones is dissolved in the dimethylbenzene or aliphatic hydrocarbon of the water that contains 5-30% and 95-70%, be heated to boiling, cool the temperature to 70 ℃-90 ℃ after, tell the water layer that contains phthalic acid with skimmer, oil reservoir is cooled to 5 ℃-25 ℃, and the elaboration naphthoquinones is separated out in condensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127954 CN1213981C (en) | 2001-07-20 | 2001-07-20 | Gaseous oxidation and liquid-solid extraction process in a low-temperature short fluidized bed to prepare 1,4-naphthaquinone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127954 CN1213981C (en) | 2001-07-20 | 2001-07-20 | Gaseous oxidation and liquid-solid extraction process in a low-temperature short fluidized bed to prepare 1,4-naphthaquinone |
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| Publication Number | Publication Date |
|---|---|
| CN1332143A true CN1332143A (en) | 2002-01-23 |
| CN1213981C CN1213981C (en) | 2005-08-10 |
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|---|---|---|---|
| CN 01127954 Expired - Fee Related CN1213981C (en) | 2001-07-20 | 2001-07-20 | Gaseous oxidation and liquid-solid extraction process in a low-temperature short fluidized bed to prepare 1,4-naphthaquinone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349941A (en) * | 2016-12-22 | 2017-11-17 | 沈秋钟 | 1,4 naphthalenedione method for preparing catalyst and 1,4 naphthalenedione manufacturing technique methods |
| CN115364846A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | Catalyst with naphthalene gas phase oxidation catalysis function and preparation method and application thereof |
| CN115703703A (en) * | 2021-08-09 | 2023-02-17 | 浙江医药股份有限公司新昌制药厂 | Method for continuously synthesizing 2-methyl-1,4-naphthoquinone |
-
2001
- 2001-07-20 CN CN 01127954 patent/CN1213981C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349941A (en) * | 2016-12-22 | 2017-11-17 | 沈秋钟 | 1,4 naphthalenedione method for preparing catalyst and 1,4 naphthalenedione manufacturing technique methods |
| CN115364846A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | Catalyst with naphthalene gas phase oxidation catalysis function and preparation method and application thereof |
| CN115703703A (en) * | 2021-08-09 | 2023-02-17 | 浙江医药股份有限公司新昌制药厂 | Method for continuously synthesizing 2-methyl-1,4-naphthoquinone |
| CN115703703B (en) * | 2021-08-09 | 2024-01-30 | 浙江芳原馨生物医药有限公司 | Method for continuously synthesizing 2-methyl-1, 4-naphthoquinone |
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|---|---|
| CN1213981C (en) | 2005-08-10 |
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