CN114471662B - Preparation of metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst and application of catalyst in synthesis of diphenolic acid - Google Patents

Preparation of metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst and application of catalyst in synthesis of diphenolic acid Download PDF

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CN114471662B
CN114471662B CN202210166211.7A CN202210166211A CN114471662B CN 114471662 B CN114471662 B CN 114471662B CN 202210166211 A CN202210166211 A CN 202210166211A CN 114471662 B CN114471662 B CN 114471662B
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邓晋
朱瑞
彭远桃
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University of Science and Technology of China USTC
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Abstract

The invention discloses a preparation method of a metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst and application thereof in synthesis of diphenolic acid, wherein-SO is used 3 H group modified nitrogen-doped carbon nano-tubes respectively encapsulate Fe, co or Ni magnetic nano-particles to obtain metal-coated sulfonated nitrogen-doped carbon nano-tube magnetic solid acid catalystAn oxidizing agent. The magnetic core of the magnetic catalyst is generated in situ in the roasting process, so that the synthesis steps of the traditional magnetic solid acid are greatly simplified, the packaging structure of the catalyst can effectively improve the stability and the service life of the catalyst, and when the magnetic core is applied to catalyzing the condensation of levulinic acid and phenol to prepare diphenolic acid, the conversion rate of the levulinic acid exceeds 99%, the yield of the obtained diphenolic acid exceeds 90%, and the isomer ratio (p, p ': o, p') of the diphenolic acid exceeds 20%.

Description

Preparation of metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst and application of catalyst in synthesis of diphenolic acid
Technical Field
The invention belongs to the technical field of diphenolic acid synthesis catalyst preparation, and particularly relates to preparation of a metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst and application of the metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst in diphenolic acid synthesis.
Background
Bisphenol a (BPA) is used industrially to synthesize materials such as polycarbonate and epoxy resin. For the past 60 s it has been used to make plastic (milk) bottles, drinking cups for infants, food and beverage (milk powder) can inside coatings. BPA is ubiquitous and has its silhouette from mineral water bottles, medical devices, and into food packaging. About 2700 million tons of BPA-containing plastics are produced worldwide each year. BPA can also cause endocrine dysregulation, can lead to obesity, impaired male reproductive function, diabetes, cardiovascular and cerebrovascular disease and even cancer. The european union considered that the baby bottles containing bisphenol a were induced to be precocious, and from 3/2 days 2011, the production of baby bottles containing chemical substance bisphenol a was prohibited. The ministry of health in China similarly announces that the sale of bisphenol A-containing infant food containers is prohibited since 2011, 9, 1.
Diphenolic Acid (DPA), an important derivative of levulinic Acid, is often used as an organic synthesis intermediate and a high polymer monomer to participate in the reaction. Because DPA has a similar molecular structure and similar physicochemical properties to BPA, DPA can be used as an analog of BPA to produce synthetic polymeric materials such as epoxy resins or polycarbonates. But one of raw materials for synthesizing the bisphenol A is low in acetone price, so that the production cost of the bisphenol A is low, and most markets are occupied. Along with the maturity of the production process of the levulinic acid and the reduction of the price, the price of the diphenolic acid is reduced, so that the substitution of the bisphenol A becomes possible; furthermore, along with the destructive effect of bisphenol a on the endocrine system of human body, some countries such as the european union have started to forbid the use of bisphenol a type materials, which also makes people pay more attention to the development of diphenolic acid as a substitute, and it is expected that diphenolic acid may occupy nearly 20% of the market share of bisphenol a in the near future. Therefore, it is necessary to develop a basic research make internal disorder or usurp for diphenolic acid and expand the application range of diphenolic acid.
Figure GDA0003931318260000011
Diphenolic acids are generally produced from levulinic acid and phenol by condensation reactions in the presence of acidic catalysts. Hydrochloric acid or sulfuric acid is generally used as a catalyst for the synthesis of diphenolic acid. Although the above catalytic strategies are useful, they still have many limitations, such as consumption of corrosive reagents, unrecoverable catalysts, harsh reaction conditions and equipment corrosion, etc. Thus, chemists are forced to develop more efficient heterogeneous catalysts. Heterogeneous catalysts for the preparation of DPA are of a wide variety, mainly
Figure GDA0003931318260000012
Acidic ionic liquid, polymer resin containing sulfonic acid group, polysiloxane catalyst containing alkyl sulfonic acid, etc. However, in the actual reaction process, it is difficult to separate the solid residue from the catalyst using the conventional separation method. The magnetic solid acid has great application prospect due to the superparamagnetic characteristic, but in the traditional preparation process of the magnetic solid acid catalyst, magnetic nanoparticles must be prepared and then wrapped. The whole process is complicated, time-consuming and energy-consuming. Therefore, the research and preparation of the magnetic solid acid catalyst which can efficiently catalyze the condensation of levulinic acid and phenol and has a green and simple preparation process is of great significance.
Figure GDA0003931318260000021
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a preparation method of a metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst and an application of the metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst in synthesis of diphenolic acid. The magnetic core of the magnetic catalyst is generated in situ in the roasting process, so that the synthesis steps of the traditional magnetic solid acid are greatly simplified, the packaging structure of the catalyst can effectively improve the stability and the service life of the catalyst, and when the magnetic core is applied to catalyzing condensation of levulinic acid and phenol to prepare diphenolic acid, the conversion rate of the levulinic acid exceeds 99%, the yield of the obtained diphenolic acid exceeds 90%, and the isomer ratio (p, p ': o, p') of the diphenolic acid exceeds 20%.
The invention relates to a preparation method of a metal-coated sulfonated nitrogen-doped carbon nano tube magnetic solid acid catalyst, which uses-SO 3 The N-doped carbon nano-tube modified by the H group respectively encapsulates magnetic nano-particles of Fe, co or Ni. It is noted that the magnetic nuclei are formed in situ during the calcination of the catalyst, and the magnetic nuclei impart excellent magnetic separation properties to the catalyst, making the separation of the catalyst from the reaction solution easier, and, in addition, -SO 3 The H group can effectively catalyze the condensation reaction of levulinic acid and phenols to generate diphenolic acid. It is worth noting that the encapsulation structure of the catalyst can effectively improve the stability of the catalyst, and the catalyst still has good stability under the acidic reaction condition.
The method specifically comprises the following steps:
step 1: dissolving Fe, co or Ni metal salt, a template agent and melamine in water, and stirring at room temperature for 1.5-3.2h to prepare suspension;
step 2: removing the solvent in the suspension obtained in the step 1, and roasting the obtained powder at high temperature for 4-6h to obtain roasted M @ NC; leaching the roasted M @ NC in an acid solution at 60-80 ℃ for 1-24h, thoroughly washing with deionized water and drying to obtain M @ NC;
and 3, step 3: placing the M @ NC obtained in the step 2 into a round-bottom flask, adding a certain amount of dichloromethane, then dropwise adding chlorosulfonic acid into the system, stirring at room temperature for reaction, thoroughly washing the obtained product with deionized water and drying to obtain the productM@NC-SO 3 And H, a catalyst.
The invention prepares the sulfonated nitrogen-doped carbon nano tube magnetic solid acid catalyst Fe @ NC-SO coated with different metals (Fe, co or Ni) by utilizing the method 3 H、Co@NC-SO 3 H or Ni @ NC-SO 3 H, -SO in catalyst 3 The content of H is 1-2.2mmol/g.
In step 1, the metal salt of Fe, co or Ni is ferric nitrate nonahydrate [ Fe (NO) 3 ) 3 ·9H 2 O]Cobalt acetate tetrahydrate [ Co (CH) 3 COO) 2 ·4H 2 O]Or nickel nitrate hexahydrate [ Ni (NO) 3 ) 2 ·6H 2 O](ii) a The template agent adopts a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) with the molecular formula of PEO-PPO-PEO (Sigma-Aldrich, EO20PO70EO20, ma = 5800).
In the step 1, the mass ratio of the metal salt of Fe, co or Ni, the template agent and the melamine is 1:1.1-2.0:2.0 to 3.0, more preferably 1:1.5:2.25.
in the step 1, the mass ratio of the metal salt of Fe, co or Ni to water is 1:40-100, more preferably 1:80.
in step 2, the solvent is removed by rotary evaporation under vacuum at 70-80 ℃.
In the step 2, the roasting parameters are 180 ℃ for 2h, 240 ℃ for 1h and 900 ℃ for 1h, and the heating rate is 2 ℃ for min -1 。
In step 2, the optimal condition for acid leaching is leaching at 80 ℃ for 12h.
In the step 3, the mass ratio of M @ NC to dichloromethane is 0.005-0.04:1, more preferably 0.02:1; the mass ratio of the M @ NC to the chlorosulfonic acid is 1.8-3.6:1, more preferably 2.7:1.
the application of the metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst prepared by the invention is used as the catalyst in the process of preparing diphenolic acid by condensing levulinic acid and phenol.
Furthermore, the reaction temperature is 60 ℃, and the reaction time is 24-48h.
Furthermore, thioglycolic acid was also added to the reaction.
In the course of the above-mentioned catalytic reaction, the conversion rate of levulinic acid exceeds 99%, the yield of the obtained diphenolic acid exceeds 90%, and the isomer ratio (p, p ': o, p') of the obtained diphenolic acid exceeds 20%.
Compared with the existing catalyst, the invention has the following advantages:
1. the magnetic core is formed in situ in the catalyst calcination process, so that the catalyst has excellent magnetic separation performance, and the catalyst and the reaction liquid are separated more easily.
2. M @ NC-SO obtained in the invention 3 The catalyst has excellent catalytic activity due to the more regular microstructure and the larger specific surface area, and the encapsulation structure of the catalyst can effectively improve the stability of the catalyst, so that the catalyst still has good stability under the acidic reaction condition.
3. Compared with the existing catalyst, the metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst (Fe @ NC-SO) prepared by the invention 3 H、Co@NC-SO 3 H or Ni @ NC-SO 3 H) The preparation process is simple, the cost is low, the method has the advantages of safe use, simple separation after use, high product selectivity and the like, and the method has remarkable progress and can be popularized and applied.
Drawings
FIG. 1 shows the magnetic solid acid catalyst (Co @ NC-SO) coated with metallic cobalt for sulfonated nitrogen doped carbon nanotubes prepared in example 1 of the present invention 3 H) The micrograph (100 nm).
FIG. 2 shows the Fe-coated S-N doped carbon nanotube magnetic solid acid catalyst (Fe @ NC-SO) prepared in example 2 of the present invention 3 H) The electron micrograph (100 nm).
FIG. 3 shows the Ni-coated S-N doped carbon nanotube magnetic solid acid catalyst (Ni @ NC-SO) prepared in example 3 of the present invention 3 H) The electron micrograph (100 nm).
FIG. 4 is Co @ NC-SO obtained in example 1 of the present invention 3 HPLC spectrogram of diphenolic acid synthesized by H catalyst.
FIG. 5 is Co @ NC-SO obtained in example 1 of the present invention 3 Method for synthesizing diphenolic acid by using H catalyst 1 H NMR spectrum.
FIG. 6 is Co @ NC-SO obtained in example 1 of the present invention 3 Method for synthesizing diphenolic acid by using H catalyst 13 C NMR spectrum.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1:
the preparation method of the sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst coated with metallic cobalt in the embodiment comprises the following steps:
step 1: cobalt acetate, templating agent and melamine were dissolved in water and the resulting mixture was stirred at room temperature for 2h and further stirred at 80 ℃ for 0.5h to produce a suspension. The cobalt acetate adopts [ Co (CH) 3 COO) 2 ·4H 2 O]The template agent adopts PEO-PPO-PEO, wherein the mass ratio of the cobalt acetate to the template agent to the melamine is 1:1.5:2.25; the mass ratio of the cobalt acetate to the water is 1:80.
step 2: the solvent in the suspension obtained in step 1 was removed by vacuum rotary evaporation, and the resulting powder was calcined at high temperature for 4-6 hours to obtain calcined Co @ NC. And leaching the roasted Co @ NC in an acid solution at 80 ℃ for 12h, thoroughly washing with deionized water and drying to obtain the Co @ NC. The high-temperature roasting mode comprises heating at 180 ℃ for 2h, heating at 240 ℃ for 1h, and heating at 900 ℃ for 1h, wherein the heating rate is 2 ℃ for min -1 。
And step 3: placing Co @ NC obtained in the step 2 into a round-bottom flask, adding a certain amount of dichloromethane, then dropwise adding a certain amount of chlorosulfonic acid into the round-bottom flask, stirring and reacting at room temperature for 48 hours, and removing the obtained product after the reaction is finishedWashing thoroughly with water and drying to obtain Co @ NC-SO 3 And H, a catalyst. The mass ratio of Co @ NC, dichloromethane and chlorosulfonic acid is 1:50:1.5.
example 2:
the preparation method of the sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst coated with metallic iron in the embodiment comprises the following steps:
step 1: iron nitrate, a templating agent and melamine were dissolved in water and the resulting mixture was stirred at room temperature for 2h and further stirred at 80 ℃ for 0.5h to produce a suspension. The ferric acetate is [ Fe (NO) 3 ) 3 ·9H 2 O]The template agent adopts PEO-PPO-PEO, wherein the mass ratio of the ferric nitrate to the template agent to the melamine is 1:1.5:2.25; the mass ratio of the ferric nitrate to the water is 1:80.
and 2, step: the solvent in the suspension obtained in step 1 is removed by vacuum rotary evaporation and the resulting powder is calcined at high temperature for 4-6 hours to obtain calcined Fe @ NC. Further leaching the roasted Fe @ NC in an acid solution at 80 ℃ for 12h, thoroughly washing with deionized water and drying to obtain Fe (@ NC.. The roasting modes at high temperature are 180 ℃ for 2h, 240 ℃ for 1h, 900 ℃ for 1h, and the heating rate is 2 ℃ for min -1 。
And step 3: the Fe @ NC obtained in step 2 was placed in a round bottom flask and a certain amount of dichloromethane was added. Then, a certain amount of chlorosulfonic acid is dripped into the round-bottom flask, the round-bottom flask is stirred and reacted for 48 hours at room temperature, and the obtained product is thoroughly washed by deionized water and dried to obtain Fe @ NC-SO 3 And H, a catalyst. The mass ratio of Fe @ NC to dichloromethane to chlorosulfonic acid is 1:50:1.5.
example 3:
the preparation method of the sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst coated with metallic nickel in the embodiment comprises the following steps:
step 1: nickel nitrate, a templating agent and melamine were dissolved in water and the resulting mixture was stirred at room temperature for 2h and further stirred at 80 ℃ for 0.5h to produce a suspension. The nickel acetate adopts [ Ni (NO) 3 ) 2 ·6H 2 O]The template agent adopts PEO-PPO-PEO, wherein the mass ratio of nickel nitrate to the template agent to melamine is 1:1.5:2.25; the mass ratio of the nickel nitrate to the water is 1:80.
step 2: the solvent in the suspension obtained in step 1 was removed by vacuum rotary evaporation, and the resulting powder was calcined at high temperature for 4-6 hours to obtain Ni @ NC after calcination. And leaching the roasted Ni @ NC in an acid solution at 80 ℃ for 12h, thoroughly washing with deionized water and drying to obtain the Ni @ NC. The high-temperature roasting mode comprises heating at 180 ℃ for 2h, heating at 240 ℃ for 1h, and heating at 900 ℃ for 1h, wherein the heating rate is 2 ℃ for min -1 。
And step 3: the ni @ nc obtained in step 2 was placed in a round bottom flask and a certain amount of dichloromethane was added. Then, adding a certain amount of chlorosulfonic acid dropwise into the round-bottom flask, stirring and reacting at room temperature for 48h, thoroughly washing the obtained product with deionized water and drying to obtain Ni @ NC-SO 3 And H, a catalyst. The mass ratio of Ni @ NC, dichloromethane and chlorosulfonic acid is 1:50:1.5.
in addition, the sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalysts coated with different metals prepared in examples 1 to 3 are used to catalyze the condensation of levulinic acid and phenol to synthesize diphenolic acid, the conversion rate of levulinic acid is detected by gas chromatography, and the yield of diphenolic acid is detected by high performance liquid chromatography.
Examples 4 to 12:
adding 1mmol of levulinic acid, 4mmol of phenol, 10mol percent of solid acid catalyst and 20mol percent of thioglycollic acid into a reaction tube provided with a magnetic stirrer, degassing the reaction tube and aerating Ar; then placing the reaction tube in a preheated oil bath, and stirring for 24 hours at 60 ℃; after completion of the reaction, the catalyst was removed with a magnet, the conversion of levulinic acid was measured by gas chromatography, and the product diphenolic acid was quantitatively analyzed by high performance liquid chromatography (table 1).
TABLE 1 Effect of different catalysts on the condensation of levulinic acid with phenol at 60 ℃ to diphenolic acid
Figure GDA0003931318260000061
For examples 4 to 12, the cobalt-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst prepared in example 1 was used to catalyze the condensation of levulinic acid and phenol to synthesize diphenolic acid, the conversion rate of levulinic acid was as high as 98%, the yield of diphenolic acid obtained was over 95%, and the isomer ratio of p, p ': o, p' was 23.7. The catalyst has extremely high catalytic activity and can meet the application requirements.

Claims (9)

1. A preparation method of a metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst is characterized by comprising the following steps:
step 1: dissolving Fe, co or Ni metal salt, a template agent and melamine in water, and stirring at room temperature for 1.5-3.2h to prepare suspension;
step 2: removing the solvent in the suspension obtained in the step 1, and roasting the obtained powder at high temperature for 4-6h to obtain roasted M @ NC; leaching the roasted M @ NC in an acid solution at 60-80 ℃ for 1-24h, thoroughly washing with deionized water and drying to obtain M @ NC;
and 3, step 3: putting the M @ NC obtained in the step 2 into a round-bottom flask, adding a certain amount of dichloromethane, then dropwise adding chlorosulfonic acid into the system, stirring and reacting at room temperature, thoroughly washing the obtained product with deionized water, and drying to obtain the M @ NC-SO 3 A H catalyst;
in the step 1, the metal salt of Fe, co or Ni is ferric nitrate nonahydrate, cobalt acetate tetrahydrate or nickel nitrate hexahydrate; the template agent adopts a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer P123 with a molecular formula of PEO-PPO-PEO.
2. The method of claim 1, wherein:
in the step 1, the mass ratio of the metal salt of Fe, co or Ni, the template agent and the melamine is 1:1.1-2.0:2.0-3.0.
3. The method of claim 1, wherein:
in the step 1, the mass ratio of the metal salt of Fe, co or Ni to water is 1:40-100.
4. The method of claim 1, wherein:
in the step 2, the roasting parameters are 180 ℃ for 2h, 240 ℃ for 1h and 900 ℃ for 1h, and the heating rate is 2 ℃ for min -1 。
5. The production method according to claim 1, characterized in that:
in the step 3, the mass ratio of M @ NC to dichloromethane is 0.005-0.04: the mass ratio of 1,M @ NC to chlorosulfonic acid is 1.8-3.6:1.
6. the method of claim 1, wherein:
in catalyst-SO 3 The content of H is 1-2.2mmol/g.
7. The application of the metal-coated sulfonated nitrogen-doped carbon nanotube magnetic solid acid catalyst obtained by the preparation method according to any one of claims 1 to 6 is characterized in that: is used as a catalyst in the process of preparing diphenolic acid by condensing levulinic acid and phenol.
8. Use according to claim 7, characterized in that:
the reaction temperature is 60 ℃, and the reaction time is 24-48h.
9. Use according to claim 7, characterized in that:
thioglycolic acid was also added to the reaction.
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