CN109876849B - 1, 4-naphthoquinone catalyst prepared by liquid-phase oxidation of naphthalene and preparation method and application thereof - Google Patents
1, 4-naphthoquinone catalyst prepared by liquid-phase oxidation of naphthalene and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst, which comprises a carrier and an active component; the carrier is a molecular sieve; the active component is transition metal oxide modified by strong acid; the mass percentage of the active component is 0.5-50% based on the mass of the catalyst. The catalyst is a catalyst for preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The invention also discloses a preparation method of the catalyst and a reaction for preparing the 1, 4-naphthoquinone by applying the catalyst through liquid phase oxidation of naphthalene, which effectively improve the conversion rate of naphthalene and the selectivity of the 1, 4-naphthoquinone, and have the advantages of mild reaction conditions, simple operation, easy preparation of the catalyst, no pollution and recyclability.
Description
Technical Field
The invention relates to a 1, 4-naphthoquinone catalyst prepared by liquid-phase oxidation of naphthalene, a preparation method and application thereof, and belongs to the field of chemical engineering.
Background
The 1, 4-naphthoquinone is an important raw material in fine chemical engineering, is an intermediate of medicine, dye, spice, pesticide, plasticizer and the like, a polymerization regulator for synthesizing rubber and resin, and is an important raw material for synthesizing a novel papermaking cooking aid. In addition, the 1, 4-naphthoquinone has excellent ultraviolet absorption performance and visible near infrared reflection function, so that the 1, 4-naphthoquinone has important significance in the aspect of textile functional dyes.
The 1, 4-naphthoquinone is synthesized by using naphthalene as a raw material mainly by a catalytic oxidation method. The oxidation method can be classified into a gas phase oxidation method and a liquid phase oxidation method according to the difference of the oxidizing agent. The gas-phase catalytic oxidation method of naphthalene is favored by researchers in industrially developed countries because 1, 4-naphthoquinone is prepared with low cost, and the by-product is mainly phthalic anhydride besides 1, 4-naphthoquinone and is easy to separate. In 1973, kawasaki chemical synthesis company of japan industrialized the high-temperature gas-phase catalytic oxidation method, but the method has severe reaction conditions and produces approximately equal amounts of phthalic anhydride as a by-product, and the selectivity of 1, 4-naphthoquinone is poor. Relatively few research reports in this aspect of China are reported. In conclusion, due to the difficulty of catalytic oxidation of naphthalene, the conversion rate of naphthalene and the selectivity of 1, 4-naphthoquinone are not high, although the industrial production of the catalytic oxidation method of gas phase and the related patents report.
The liquid phase oxidation method is the main method for producing 1, 4-naphthoquinone at present in China. Compared with a gas phase oxidation method, the method has mature process and relatively high conversion rate and selectivity of the product. The catalyst commonly used in actual industrial production is a heavy metal catalyst such as chromium oxide, and a stoichiometric amount of a heavy metal-based catalyst such as chromium oxide is required to participate in the reaction system. In addition, glacial acetic acid is often used as a solvent in a reaction system, so that the method has strong corrosivity and high requirements on the material of equipment. The liquid phase oxidation method is adopted, the reaction condition is mild, the selectivity to the naphthoquinone is good, and the main defects of the existing liquid phase oxidation method are that in the reaction system, stoichiometric chromium oxide and other heavy metal-based catalysts are required to participate, so that a large amount of heavy metal-containing industrial wastewater is generated in industrial production, the wastewater treatment process is difficult and complicated, the environment can be seriously polluted, meanwhile, the amount of solvent required by the reaction system is large, the concentration of the generated naphthoquinone is low, and great difficulty is brought to the separation of the naphthoquinone. In order to realize clean production of 1, 4-naphthoquinone, a liquid phase oxidation catalyst with good activity and high selectivity needs to be developed.
Disclosure of Invention
According to one aspect of the present invention, a catalyst is provided. The catalyst can be used for the reaction of preparing 1, 4-naphthoquinone by liquid-phase oxidation of naphthalene, effectively improves the conversion rate of naphthalene and the selectivity of 1, 4-naphthoquinone, and has good industrial application prospect.
The catalyst comprises a carrier and an active component;
the carrier is a molecular sieve;
the active component is transition metal oxide modified by strong acid;
the mass percentage of the active component is 0.5-50% based on the mass of the catalyst.
The catalyst is a 1, 4-naphthoquinone catalyst prepared by liquid-phase oxidation of naphthalene.
In the catalyst, the active component is selected from at least one of transition metal titanium (Ti) oxide, vanadium (V) oxide, manganese (Mn) oxide, iron (Fe) oxide, cobalt (Co) oxide, nickel (Ni) oxide and copper (Cu) oxide.
Preferably, the mass percentage of the transition metal oxide is 0.5-50% based on the mass of the catalyst. More preferably, the mass percentage of the transition metal oxide is 2% to 20% based on the mass of the catalyst. More preferably, the mass percentage of the transition metal oxide is 10% to 20% based on the mass of the catalyst.
Preferably, the molecular sieve is at least one selected from HY, Beta, MOR and ZSM-5 molecular sieves.
Preferably, the strong acid is concentrated sulfuric acid.
According to another aspect of the present invention, there is provided a method for preparing the above catalyst, specifically comprising the steps of:
a) preparing a precursor solution from transition metal salt;
b) loading the precursor solution prepared in the step a) by using a molecular sieve as a carrier and adopting an isometric impregnation method;
c) drying and roasting the molecular sieve catalyst loaded with transition metal in the step b);
d) loading strong acid by using the molecular sieve loaded with transition metal in the step c) as a carrier and adopting an excessive impregnation method;
e) drying and roasting the molecular sieve modified by the strong acid in the step d) to prepare the naphthalene liquid phase oxidation catalyst.
According to another aspect of the invention, a reaction method for preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene is provided, wherein naphthalene, a catalyst and an organic solvent are sequentially added into a reaction vessel, and hydrogen peroxide is used as an oxidant to catalyze and oxidize naphthalene to prepare 1, 4-naphthoquinone.
Preferably, the reaction temperature is 40-150 ℃, and the reaction time is 2-10 hours.
As a specific embodiment, the specific reaction process is as follows: adding a certain amount of naphthalene, a catalyst and an acetic acid solvent into a reaction vessel in sequence, reacting for 2-10 hours at the temperature of 40-150 ℃ by taking hydrogen peroxide as an oxidant, and preparing 1, 4-naphthoquinone by catalytic oxidation of naphthalene.
The beneficial effects of the invention include:
the liquid phase oxidation catalyst of naphthalene prepared by the invention is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene, and effectively improves the conversion rate of naphthalene and the selectivity of 1, 4-naphthoquinone, thereby having better industrial application prospect.
Detailed Description
The following examples are merely illustrative of the present invention and the present invention is not limited to these examples. All the similar structures and similar changes of the invention are included in the protection scope of the invention.
Example 1
Weighing 10gHY molecular sieve carrier, and 0.5mol/L Fe (NO) at room temperature3)39H2Soaking in O water solution for 0.5h, wherein the volume of the solution is measured according to the mass content of the ferric oxide on the molecular sieve of 10%. Drying at room temperature, drying at 120 deg.C for 10h, placing in muffle furnace, heating to 500 deg.C, and roasting in air for 4h to obtain Fe2O3HY. Weighing a certain amount of Fe2O3/HY, soaking in diluted concentrated sulfuric acid solution for 12h, drying, and roasting to obtain concentrated sulfuric acid modified Fe2O3and/HY, as catalyst 1.
The catalyst 1 prepared above is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 35.6%, and the selectivity of 1, 4-naphthoquinone was 78.2%.
Example 2
Weighing 10gHY molecular sieve carrier, and 0.5mol/L Fe (NO) at room temperature3)39H2O aqueous solutionThe solution is dipped for 0.5h, and the volume of the solution is measured according to the mass content of the ferric oxide on the molecular sieve of 15 percent. Drying at room temperature, drying at 120 deg.C for 10h, placing in muffle furnace, heating to 500 deg.C, and roasting in air for 4h to obtain Fe2O3HY. Weighing a certain amount of Fe2O3/HY, soaking in diluted concentrated sulfuric acid solution for 12h, drying, and roasting to obtain concentrated sulfuric acid modified Fe2O3and/HY, as catalyst 2.
The catalyst 2 prepared above is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 45.2%, and the selectivity of 1, 4-naphthoquinone was 80.2%.
Example 3
Weighing 10g HY molecular sieve carrier, and 0.5mol/L Fe (NO) at room temperature3)39H2Soaking in O water solution for 0.5h, wherein the volume of the solution is measured according to the mass content of the ferric oxide on the molecular sieve of 20%. Drying at room temperature, drying at 120 deg.C for 10h, placing in muffle furnace, heating to 500 deg.C, and roasting in air for 4h to obtain Fe2O3HY. Weighing a certain amount of Fe2O3/HY, soaking in diluted concentrated sulfuric acid solution for 12h, drying, and roasting to obtain concentrated sulfuric acid modified Fe2O3HY, as catalyst 3.
The catalyst 3 prepared above is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 47.3%, and the selectivity of 1, 4-naphthoquinone was 79.2%.
Example 4
Weighing 10g HY molecular sieve carrier, and 0.5mol/L Co (NO) at room temperature3)26H2Soaking in O water solution for 0.5 hr, wherein the volume of the solution is determined by molecular sieveThe cobalt oxide is measured in an amount of 10% by mass. Drying at room temperature, drying at 120 deg.C for 10 hr, heating to 500 deg.C in muffle furnace, and calcining in air for 4 hr to obtain Co2O3HY. Weighing a certain amount of Co2O3/HY, soaking in diluted concentrated sulfuric acid solution for 12h, drying, and calcining to obtain Co modified by concentrated sulfuric acid2O3and/HY, as catalyst 4.
The catalyst 4 prepared above is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dripping 2mL of 30% hydrogen peroxide and keeping
Reacting for 6 hours at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 27.3%, and the selectivity of 1, 4-naphthoquinone was 76.3%.
Example 5
Weighing 10g Beta molecular sieve carrier, and 0.5mol/L Fe (NO) at room temperature3)39H2Soaking in O water solution for 0.5h, wherein the volume of the solution is measured according to the mass content of the ferric oxide on the molecular sieve of 10%. Drying at room temperature, drying at 120 deg.C for 10h, placing in muffle furnace, heating to 500 deg.C, and roasting in air for 4h to obtain Fe2O3a/Beta. Weighing a certain amount of Fe2O3Beta, soaking in diluted concentrated sulfuric acid solution for 12h, drying and roasting to obtain concentrated sulfuric acid modified Fe2O3and/Beta, noted as catalyst 5.
The catalyst 5 prepared above is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 24.6%, and the selectivity of 1, 4-naphthoquinone was 85.2%.
Example 6
Weighing 10g MOR molecular sieve carrier, and 0.5mol/L Fe (NO) at room temperature3)39H2Soaking in O water solution for 0.5 hr, wherein the volume of the solution is determined by molecular sieveThe mass content of the ferric oxide is 10 percent. Drying at room temperature, drying at 120 deg.C for 10h, placing in muffle furnace, heating to 500 deg.C, and roasting in air for 4h to obtain Fe2O3/MOR. Weighing a certain amount of Fe2O3/MOR, soaking in diluted concentrated sulfuric acid solution for 12h, drying and roasting to obtain concentrated sulfuric acid modified Fe2O3the/MOR, noted as catalyst 6.
The catalyst 6 prepared above is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography. As a result, the conversion of naphthalene was 18.6%, and the selectivity of 1, 4-naphthoquinone was 68.2%.
Example 7
Weighing 10g ZSM-5 molecular sieve carrier, and 0.5mol/L Fe (NO) at room temperature3)39H2Soaking in O water solution for 0.5h, wherein the volume of the solution is measured according to the mass content of the ferric oxide on the molecular sieve of 10%. Drying at room temperature, drying at 120 deg.C for 10h, placing in muffle furnace, heating to 500 deg.C, and roasting in air for 4h to obtain Fe2O3ZSM-5. Weighing a certain amount of Fe2O3ZSM-5, soaking in diluted concentrated sulfuric acid solution for 12h, drying and roasting to obtain concentrated sulfuric acid modified Fe2O3ZSM-5, noted catalyst 7.
The prepared catalyst is used for the reaction of preparing 1, 4-naphthoquinone by liquid phase oxidation of naphthalene. The specific implementation process is as follows: a250 mL round-bottom flask was charged with 0.8g of naphthalene, 25mL of acetic acid, and 0.2g of a catalyst. Heating to 60 ℃, dropwise adding 2mL of 30% hydrogen peroxide, and reacting for 6h at constant temperature. The product composition was analyzed by gas chromatography, and as a result, the conversion of naphthalene was 18.6% and the selectivity of 1, 4-naphthoquinone was 58.9%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (5)
1. A catalyst, characterized in that the catalyst comprises a support and an active component;
the carrier is a molecular sieve;
the active component is transition metal oxide modified by strong acid;
the molecular sieve is selected from at least one of HY molecular sieve, Beta molecular sieve, MOR molecular sieve and ZSM-5 molecular sieve;
the strong acid is concentrated sulfuric acid;
the transition metal oxide is selected from at least one of titanium oxide, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide and copper oxide;
the mass percentage of the active component is 2-20% based on the mass of the catalyst;
the preparation method of the catalyst at least comprises the following steps:
a) preparing a precursor solution from transition metal salt;
b) loading the precursor solution prepared in the step a) by using a molecular sieve as a carrier and adopting an isometric impregnation method;
c) drying and roasting the molecular sieve catalyst loaded with transition metal in the step b);
d) loading strong acid by using the molecular sieve loaded with transition metal in the step c) as a carrier and adopting an excessive impregnation method;
e) drying and roasting the molecular sieve modified by the strong acid in the step d) to prepare the catalyst.
2. A reaction method for preparing 1, 4-naphthoquinone by liquid-phase oxidation of naphthalene is characterized in that the catalyst of claim 1 is used as a catalyst for the liquid-phase catalytic oxidation reaction of naphthalene.
3. The reaction process of claim 2, comprising: naphthalene, a catalyst and an organic solvent are sequentially added into a reaction vessel, and the 1, 4-naphthoquinone is prepared by catalytic oxidation of the naphthalene by taking hydrogen peroxide as an oxidant.
4. The reaction method according to claim 3, wherein the reaction temperature is 40 to 150 ℃ and the reaction time is 2 to 10 hours.
5. The reaction process of claim 3, wherein the organic solvent is acetic acid.
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| CN101462066A (en) * | 2008-03-11 | 2009-06-24 | 郑州大学 | Catalyst for preparing naphthaquinone and preparation method thereof |
| CN102924266A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Method for preparing phthalic acid by xylol co-oxidation catalyst system |
| CN103570520A (en) * | 2013-08-21 | 2014-02-12 | 山东鲁抗舍里乐药业有限公司 | Benzoquinones compound, preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1559682A (en) * | 2004-03-05 | 2005-01-05 | 华东师范大学 | Bitransition metal modified molecular sieve and its preparation and use |
| CN101462066A (en) * | 2008-03-11 | 2009-06-24 | 郑州大学 | Catalyst for preparing naphthaquinone and preparation method thereof |
| CN102924266A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Method for preparing phthalic acid by xylol co-oxidation catalyst system |
| CN103570520A (en) * | 2013-08-21 | 2014-02-12 | 山东鲁抗舍里乐药业有限公司 | Benzoquinones compound, preparation method and application thereof |
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