CN110562931B - Method for improving hydrogenation rate and hydrogen peroxide yield of alkyl anthraquinone derivative - Google Patents

Method for improving hydrogenation rate and hydrogen peroxide yield of alkyl anthraquinone derivative Download PDF

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CN110562931B
CN110562931B CN201910784031.3A CN201910784031A CN110562931B CN 110562931 B CN110562931 B CN 110562931B CN 201910784031 A CN201910784031 A CN 201910784031A CN 110562931 B CN110562931 B CN 110562931B
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anthraquinone
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orthosilicate
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王涖
马青青
刘国柱
张香文
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Tianjin University
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
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Abstract

The invention provides a method for improving the hydrogenation rate and the hydrogen peroxide yield of alkyl anthraquinone derivatives, wherein a supported palladium catalyst containing a hydrophobic functional group is used in the reaction, and the preparation method of the catalyst comprises the following steps: dissolving a template agent under an acidic condition, then dropwise adding n-silanol orthosilicate, stirring for a certain time, adding alkyl trialkoxysilane, and continuing stirring; then processing the mixture in a closed container at 80-120 ℃ for 24-72h, and filtering to obtain a solid sample; removing the template agent from the solid sample, filtering, washing and drying to obtain a carrier, soaking the carrier in palladium, roasting at 200-300 ℃, and reducing to obtain the catalyst. The catalyst is particularly suitable for hydrogenation reaction of long-side-chain macromolecular alkylanthraquinone derivatives, and the longer the side chain is, the better the catalytic effect is.

Description

Method for improving hydrogenation rate and hydrogen peroxide yield of alkyl anthraquinone derivative
Technical Field
The invention belongs to the field of hydrogen peroxide preparation, and particularly relates to a method for improving the hydrogenation rate of alkyl anthraquinone derivatives and the yield of hydrogen peroxide.
Background
Hydrogen peroxide (H) 2 O 2 ) Also called as hydrogen peroxide, is a colorless transparent liquid and is an important chemical product. At present, the anthraquinone process is almost the only industrial process for the production of hydrogen peroxide. Compared with other preparation methods, the preparation method has the advantages of low production cost, easy large-scale production and the like. The anthraquinone process mainly comprises four procedures of anthraquinone derivative (also called as a working carrier) hydrogenation, hydrogenated anthraquinone derivative oxidation, hydrogen peroxide extraction and anthraquinone derivative working solution regeneration. Wherein, the hydrogenation of anthraquinone derivatives is the core step of the anthraquinone process, which is related to the production cost of the product hydrogen peroxide.
The hydrogenation of anthraquinone derivatives mostly adopts supported palladium catalysts, and the selection of the carrier is crucial. At present, the carrier of the anthraquinone derivative hydrogenation catalyst mainly comprises aluminum oxide and silicon dioxide. Compared with alumina, the silica-supported Pd catalyst has high selectivity, less degradation products and lower activity.
It would be desirable to provide a process for increasing the hydrogenation rate and hydrogen peroxide yield of alkylanthraquinone derivatives.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention provides a method for improving the hydrogenation rate and the hydrogen peroxide yield of alkyl anthraquinone derivatives, wherein a supported palladium catalyst containing a hydrophobic functional group is used in the reaction, and the preparation method of the catalyst comprises the following steps:
dissolving a template agent in water under an acidic condition, then dropwise adding n-silanol orthosilicate, stirring for a certain time, adding alkyl trialkoxysilane, and continuing stirring; then carrying out hydrothermal treatment on the mixture in a closed container at the temperature of 80-120 ℃ for 24-72h, and filtering to obtain a solid sample;
and removing the template from the solid sample, filtering, washing and drying to obtain a carrier, soaking the carrier in palladium, roasting at 200-300 ℃, and reducing to obtain the catalyst.
Preferably, the alkanol orthosilicate is selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, or butyl orthosilicate.
Preferably, the alkyltrialkoxysilane is selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, propyltrialkoxysilane, and butyltrialkoxysilane.
Preferably, the alkyltrialkoxysilane is selected from the group consisting of alkyltrimethoxysilane, alkyltriethoxysilane, alkyltripropoxysilane, and alkyltributoxysilane.
Preferably, the composition of the alkanol orthosilicate, alkyltrialkoxysilane in the mixture is the alkanol orthosilicate: alkyltrialkoxysilane = (1-x): x, where x =0.05-0.2, the above ratios being molar ratios.
Preferably, the templating agent is selected from the group consisting of triblock copolymer P123, triblock copolymer F127, cetyltrimethylammonium bromide.
Preferably, the catalyst comprises:
the mesoporous silica molecular sieve carrier has regular hexagonal straight pore channels and a specific surface area of 600-1000m 2 Per g, the aperture is 4.6-30nm, and the thickness of the hole wall is 3.1-6.0nm;
a hydrophobic group grown on the support, and the hydrophobic group is selected from alkyl or alkoxy;
and metal palladium particles dispersed on the catalyst, wherein the mass of the palladium accounts for 0.5-1.5wt% of the mass of the mesoporous silica, and the diameter of the metal palladium particles is 3-5nm.
Preferably, the hydrogenation rate and the yield of hydrogen peroxide are increased by increasing the chain length of the alkyl group in the alkylanthraquinone derivative.
Wherein the hydrophobic group in the catalyst is selected from alkyl or alkoxy, and alkyl or alkoxy from alkyl trialkoxysilane. And roasting at the temperature of between 200 and 300 ℃ to prevent the hydrophobic functional groups in the catalyst from being roasted.
Preferably, the reduction temperature is 100 to 300 ℃.
Preferably, the reduction temperature is 150 to 300 ℃.
Preferably, the reduction temperature is 150 to 250 ℃.
Preferably, the stirring is carried out for 0.5 to 4 hours, and the continuous stirring is carried out for 20 to 30 hours.
Preferably, the method for removing the template agent is to treat the sample under ethanol reflux conditions for 8-24h.
Preferably, the composition of the alkanol orthosilicate, the alkyltrialkoxysilane and the template agent in the mixture is the alkanol orthosilicate: alkyl trialkoxysilane: the template agent = (1-x): x: 0.015-0.03, wherein x =0.05-0.2, and the above ratio is a molar ratio.
Preferably, the alkyl anthraquinone derivative is selected from one or more of 2-Ethyl Anthraquinone (EAQ), 2-tert-butyl anthraquinone (TBAQ), 2-Amyl Anthraquinone (AAQ), tetrahydro 2-ethyl anthraquinone (H4 EAQ), tetrahydro 2-tert-butyl anthraquinone (H4 TBAQ) and tetrahydro 2-amyl anthraquinone (H4 AAQ).
The invention has the following beneficial effects:
1. the invention provides a method for improving the hydrogenation rate and the hydrogen peroxide yield of alkyl anthraquinone derivatives by using a supported palladium catalyst containing hydrophobic groups. The catalyst is particularly suitable for hydrogenation reaction of long-side-chain macromolecular alkylanthraquinone derivatives, and the longer the side chain is, the better the catalytic effect is.
2. According to the invention, the hydrophobic group modified mesoporous silica molecular sieve carrier is synthesized in one step by a copolycondensation method, and the distribution and the content of the hydrophobic group in the mesoporous silica molecular sieve carrier are regulated and controlled by changing the prehydrolysis time of the n-silanol orthosilicate and the addition of the alkyl trialkoxysilane in the synthesis process, so that the hydrophobicity of the mesoporous silica molecular sieve carrier is improved.
3. When the supported palladium catalyst containing the hydrophobic group is used in the hydrogenation reaction of the alkyl anthraquinone derivative, the hydrogenation rate and the hydrogen peroxide yield can be improved, and the yield of degradation products is reduced.
4. The load type palladium catalyst containing the hydrophobic group has less noble metal consumption, and has high activity and high selectivity when used in the hydrogenation reaction of the alkyl anthraquinone derivative.
Drawings
Table 1 shows the carbon content, water contact angle, zeta potential of the catalysts prepared in examples 1 to 4 and comparative example 1.
Table 2 shows the results of example 5 for hydrogenation rate, hydrogen peroxide yield, and degradent yield.
FIG. 1 is a transmission electron micrograph of catalyst C1 prepared in example 1; the lower left corner of the drawing is the particle size distribution diagram (D: particle size (nm); F: percent) of the Pd particles.
FIG. 2 is a transmission electron micrograph of catalyst C2 prepared in example 2; the lower left corner of the drawing is the particle size distribution diagram (D: particle size (nm); F: percent) of the Pd particles.
FIG. 3 is a transmission electron micrograph of catalyst C3 prepared in example 3; the lower left corner of the drawing is the particle size distribution diagram (D: particle size (nm); F: percent) of the Pd particles.
FIG. 4 is a transmission electron micrograph of catalyst C4 prepared in example 4; the lower left corner of the drawing is the particle size distribution diagram (D: particle size (nm); F: percent) of the Pd particles.
FIG. 5 is a transmission electron micrograph of the catalyst DC prepared in comparative example 1; the lower left corner of the drawing is the particle size distribution diagram (D: particle size (nm); F: percent) of the Pd particles.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Example 1
2.0g of triblock polymer (Pluronic P123) were dissolved in 75mL of 1.6mol/L HCl solution and stirred at 40 ℃ for 1h; then, dropwise adding Tetraethoxysilane (TEOS), continuously stirring for 1h, then adding Propyltriethoxysilane (PTES), wherein the molar composition of TEOS, PTES and P123 in the mixture is TEOS: PTES: P123= 0.95; then transferring the mixture into an autoclave with a polytetrafluoroethylene lining, treating the mixture at 100 ℃ for 48 hours, and filtering the mixture to obtain a solid sample; in order to remove the template agent P123, the sample is treated for 24 hours under the ethanol reflux condition; and (2) filtering, washing and drying to obtain a carrier, and soaking the obtained carrier in palladium in the same volume, roasting at 250 ℃, and reducing in hydrogen atmosphere at 200 ℃ to obtain the hydrophobic group-containing supported palladium catalyst, which is marked as C1.
FIG. 1 is a transmission electron micrograph of the sample C1 obtained, as can be seen from FIG. 1: the sample presents a regular P6mm ordered mesoporous structure, pd particles are uniformly dispersed on SBA-15, and the particle size is about 4.6nm.
The carbon content, water contact angle and zeta potential of catalyst C1 are shown in Table 1.
Example 2
2.0g of triblock polymer (Pluronic P123) were dissolved in 75mL of 1.6mol/L HCl solution and stirred at 40 ℃ for 1h; then, dropwise adding Tetraethoxysilane (TEOS), stirring for 2 hours, adding Propyltriethoxysilane (PTES), wherein the molar composition of TEOS, PTES and P123 in the mixture is TEOS: PTES: P123=0.95: 0.017, and stirring for 24 hours continuously; then transferring the mixture into an autoclave with a polytetrafluoroethylene lining, treating the mixture at 100 ℃ for 48 hours, and filtering the mixture to obtain a solid sample; in order to remove the template agent P123, the sample is treated for 24 hours under the ethanol reflux condition; and (3) filtering, washing and drying to obtain a carrier, and soaking the obtained carrier in palladium in the same volume, roasting at 300 ℃ and reducing at 250 ℃ in hydrogen atmosphere to obtain the hydrophobic group-containing supported palladium catalyst, which is marked as C2.
Fig. 2 is a transmission electron micrograph of the sample C2 obtained, as can be seen from fig. 2: the sample presents a regular P6mm ordered mesoporous structure, pd particles are uniformly dispersed on SBA-15, and the particle size is about 4.6nm.
Further, the carbon content, water contact angle, zeta potential, specific surface area, pore volume and pore diameter of catalyst C2 are shown in table 1.
Example 3
2.0g of triblock polymer (Pluronic P123) were dissolved in 75mL of 1.6mol/L HCl solution and stirred at 40 ℃ for 1h; then, dropwise adding Tetraethoxysilane (TEOS), continuously stirring for 4h, then adding Propyltriethoxysilane (PTES), wherein the molar composition of TEOS, PTES and P123 in the mixture is TEOS: PTES: P123=0.95: 0.017, and continuously stirring for 24h; then transferring the mixture into an autoclave with a polytetrafluoroethylene lining, treating the mixture at 100 ℃ for 48 hours, and filtering the mixture to obtain a solid sample; in order to remove the template agent P123, the sample is treated for 24 hours under the ethanol reflux condition; and (2) filtering, washing and drying to obtain a carrier, and soaking the obtained carrier in palladium in the same volume, roasting at 300 ℃, and reducing in hydrogen atmosphere at 150 ℃ to obtain the hydrophobic group-containing supported palladium catalyst, which is marked as C3.
Fig. 3 is a transmission electron micrograph of the sample C3 obtained, as can be seen from fig. 3: the sample presents a regular P6mm ordered mesoporous structure, pd particles are uniformly dispersed on SBA-15, and the particle size is about 4.7nm.
The carbon content, water contact angle and zeta potential of catalyst C3 are shown in Table 1.
Example 4
2.0g of triblock polymer (Pluronic P123) were dissolved in 75mL of 1.6mol/L HCl solution and stirred at 40 ℃ for 1h; then, dropwise adding Tetraethoxysilane (TEOS), stirring for 2 hours, adding Propyltriethoxysilane (PTES), wherein the molar composition of TEOS, PTES and P123 in the mixture is TEOS: PTES: P123= 0.9; then transferring the mixture into an autoclave with a polytetrafluoroethylene lining, treating the mixture at 100 ℃ for 48 hours, and filtering the mixture to obtain a solid sample; in order to remove the template agent P123, the sample is treated for 24 hours under the ethanol reflux condition; and (2) filtering, washing and drying to obtain a carrier, and soaking the obtained carrier in palladium in the same volume, roasting at 200 ℃, and reducing in hydrogen atmosphere at 150 ℃ to obtain the hydrophobic group-containing supported palladium catalyst, which is marked as C4.
Fig. 4 is a transmission electron micrograph of the sample C4 obtained, as can be seen from fig. 4: the sample presents a regular P6mm ordered mesoporous structure, the Pd particles are uniformly dispersed on the SBA-15, and the particle size is about 4.2nm.
The carbon content, water contact angle and zeta potential of catalyst C4 are shown in Table 1.
Comparative example 1
2.0g of triblock polymer (Pluronic P123) were dissolved in 75mL of 1.6mol/L HCl solution and stirred at 40 ℃ for 2h; then, dropwise adding Tetraethoxysilane (TEOS), wherein the molar composition of TEOS, PTES and P123 in the mixture is 0.017 percent, namely TEOS: P123=1, and continuously stirring for 24 hours; then transferring the mixture into an autoclave with a polytetrafluoroethylene lining, treating the mixture at 100 ℃ for 48 hours, and filtering the mixture to obtain a solid sample; in order to remove the template agent P123, the sample is treated for 24 hours under the ethanol reflux condition; and (3) filtering, washing and drying to obtain a carrier, and soaking palladium in the obtained carrier in the same volume, roasting at 300 ℃, and reducing at 250 ℃ in hydrogen atmosphere to obtain the supported palladium catalyst, which is marked as DC.
Fig. 5 is a transmission electron micrograph of the sample DC obtained, as can be seen from fig. 5: the sample presents a regular P6mm ordered mesoporous structure, the Pd particles are uniformly dispersed on the SBA-15, and the particle size is about 4.3nm.
Further, the carbon content, water contact angle and zeta potential of the catalyst DC are shown in Table 1.
TABLE 1
Figure BDA0002177447220000061
Example 5
Experiment of catalytic Effect
The hydrophobic group-containing supported palladium catalyst prepared in the above examples 1 to 2 and the catalyst prepared in comparative example 1 were subjected to catalytic hydrogenation of alkylanthraquinone derivatives: 0.2g of Pd catalyst and 30mL of 0.38mol/L alkylanthraquinone derivative as working carriers were added to a high-pressure reactor using a tank reactor, and reacted at 60 ℃ and 0.3MPa, the experimental results are shown in Table 2.
TABLE 2
Figure BDA0002177447220000062
As can be seen from Table 2, when the catalyst is used in the catalytic hydrogenation reaction of 2-Ethylanthraquinone (EAQ), 2-tert-butylanthraquinone (TBAQ) and 2-amylanthraquinone (AAQ), the catalysts C1 and C2 show a significantly faster hydrogenation rate and a higher hydrogen peroxide yield than the catalyst DC under the same working carrier. In most reactions, the yields of degradants and by-product tetrahydroanthraquinone decreased, indicating an increase in catalyst selectivity.
Specifically, compared with the catalyst DC, when the working carrier is 2-Ethyl Anthraquinone (EAQ), the hydrogenation rate of the catalyst C2 is improved by 24.57%, and the yield of hydrogen peroxide is improved by 24.1%; when the working carrier is 2-tert-butyl anthraquinone (TBAQ), the hydrogenation rate is improved by 44.1 percent, and the hydrogen peroxide yield is improved by 44 percent; when the working carrier is 2-amylanthraquinone, the hydrogenation rate is improved by 103.7 percent, and the yield of the hydrogen peroxide is improved by 105.4 percent. When the working carrier was changed from 2-t-butylanthraquinone to 2-amylanthraquinone, the hydrogenation rate and the hydrogen peroxide yield were increased, which indicates that the hydrogenation rate and the hydrogen peroxide yield were increased by increasing the chain length of the alkyl group in the alkylanthraquinone derivative.
In summary, it can be seen that: the supported palladium catalyst containing the hydrophobic functional group has a relatively good catalytic effect, is simple in preparation method, controllable in structure, suitable for industrial production, and has a use value and an application prospect.
Example 6
This example uses methyl orthosilicate, propyl orthosilicate, or butyl orthosilicate instead of ethyl orthosilicate, and propyl trimethoxysilane, propyl tripropoxysilane, propyl tributoxysilane, methyl trimethoxysilane, methyl triethoxysilane, methyl tripropoxysilane, methyl tributoxysilane instead of propyl triethoxysilane, respectively, and the composition of alkanol orthosilicate, alkyltrialkoxysilane, templating agent in the mixture is alkanol orthosilicate: alkyl trialkoxysilane: template =0.8, and the above ratio is a molar ratio, and other steps are the same as in example 1, to prepare a plurality of hydrophobic functional group-containing supported palladium catalysts of the present invention, which have similar structures and catalytic effects to those in examples 1 to 4 and are not described again.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. A method for improving the hydrogenation rate and the hydrogen peroxide yield of alkyl anthraquinone derivatives, which is characterized in that a supported palladium catalyst containing hydrophobic functional groups is used in the reaction, and the preparation method of the catalyst is as follows:
dissolving a template agent in water under an acidic condition, then dropwise adding n-silanol orthosilicate, stirring for a certain time, adding alkyl trialkoxysilane, and continuing stirring; then carrying out hydrothermal treatment on the mixture in a closed container at the temperature of 80-120 ℃ for 24-72h, and filtering to obtain a solid sample;
removing the template agent from the solid sample, filtering, washing and drying to obtain a carrier, soaking the carrier in palladium, roasting at 200-300 ℃, and reducing to obtain the catalyst;
the composition of the orthosilicic acid alkanol ester and the alkyl trialkoxy silane in the mixture is the orthosilicic acid alkanol ester: alkyltrialkoxysilane = (1-x): x, wherein x =0.05-0.2, the above ratios are molar ratios;
the stirring is carried out for 0.5 to 4 hours, and the continuous stirring is carried out for 20 to 30 hours.
2. The method of claim 1, wherein the alkanol orthosilicate is selected from the group consisting of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate.
3. The method according to claim 1, characterized in that the alkyltrialkoxysilane is selected from the group consisting of methyltrialkoxysilane, ethyltrialkoxysilane, propyltrialkoxysilane, or butyltrialkoxysilane.
4. The method according to claim 1, characterized in that the alkyltrialkoxysilane is selected from the group consisting of alkyltrimethoxysilane, alkyltriethoxysilane, alkyltripropoxysilane or alkyltributoxysilane.
5. The method of claim 1, wherein the templating agent is selected from the group consisting of triblock copolymer P123, triblock copolymer F127, and cetyltrimethylammonium bromide.
6. The method of claim 1, wherein the catalyst comprises:
the mesoporous silica molecular sieve carrier has regular hexagonal straight pore channels and a specific surface area of 600-1000m 2 G, the aperture is 4.6-30nm, and the thickness of the hole wall is 3.1-6.0nm;
a hydrophobic group grown on the support, and the hydrophobic group is selected from alkyl or alkoxy;
and metal palladium particles dispersed on the catalyst, wherein the mass of the palladium accounts for 0.5-1.5wt% of the mass of the mesoporous silica, and the diameter of the metal palladium particles is 3-5nm.
7. The method as claimed in claim 6, wherein the hydrogenation rate and the yield of hydrogen peroxide are increased by increasing the chain length of the alkyl group in the alkylanthraquinone derivative.
8. The method according to claim 6, wherein the alkyl anthraquinone derivative is selected from one or more of 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-amyl anthraquinone, tetrahydro-2-ethyl anthraquinone, tetrahydro-2-tert-butyl anthraquinone, and tetrahydro-2-amyl anthraquinone.
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CN1165111A (en) * 1996-04-03 1997-11-19 三菱瓦斯化学株式会社 Hydrogenation catalyst for production of hydrogen peroxide, and method for prpearation of same
CN101015797A (en) * 2007-02-28 2007-08-15 傅骐 Preparing method of palladium catalyst with alkali resistance performance for producing hydrogen dioxide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1165111A (en) * 1996-04-03 1997-11-19 三菱瓦斯化学株式会社 Hydrogenation catalyst for production of hydrogen peroxide, and method for prpearation of same
CN101015797A (en) * 2007-02-28 2007-08-15 傅骐 Preparing method of palladium catalyst with alkali resistance performance for producing hydrogen dioxide

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