CN111203217B - Hydrogenation catalyst, preparation method and application thereof in p-tert-butylphenol hydrogenation - Google Patents

Hydrogenation catalyst, preparation method and application thereof in p-tert-butylphenol hydrogenation Download PDF

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CN111203217B
CN111203217B CN202010164143.1A CN202010164143A CN111203217B CN 111203217 B CN111203217 B CN 111203217B CN 202010164143 A CN202010164143 A CN 202010164143A CN 111203217 B CN111203217 B CN 111203217B
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hydrogenation catalyst
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CN111203217A (en
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赵欣
姜志成
代红涛
方子来
薛勇勇
林少宁
张鹏
曾伟
王磊
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Wanhua Chemical Group Co Ltd
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6567—Rhenium
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
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    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
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Abstract

The invention provides a hydrogenation catalyst, a preparation method and application thereof in p-tert-butylphenol hydrogenation, wherein the preparation method of the catalyst comprises the following steps: 1) reacting tetra-aldehyde tetraphenylethylene with a diamine compound, and filtering to obtain an organic ball cage carrier; 2) preparing an active component: respectively preparing salt solutions of nano palladium and nano magnetic rhenium as active components; 3) and mixing and refluxing the carrier and the active component to obtain the hydrogenation catalyst. The hydrogenation catalyst prepared by the method has good catalytic activity and high product selectivity in a reaction system for preparing cis-p-tert-butylcyclohexanol by hydrogenating p-tert-butylphenol.

Description

Hydrogenation catalyst, preparation method and application thereof in p-tert-butylphenol hydrogenation
Technical Field
The invention relates to a catalyst, in particular to a hydrogenation catalyst, a preparation method and application thereof in p-tert-butylphenol hydrogenation, belonging to the technical field of catalytic hydrogenation.
Background
Cis-tert-butylcyclohexanol is an important intermediate for synthesis of pesticides, medicines, liquid crystals and perfumes, and is widely applied to the field of perfume synthesis, such as synthesis of cis-tert-butylcyclohexyl acetate. Cis-acetic acid p-tert-butyl cyclohexyl ester has fragrance of costustoot and iris flowers, is a raw material of high-grade spices, essence and perfumed soap, but the trans-isomer of the cis-acetic acid p-tert-butyl cyclohexyl ester is greatly different from the taste of the cis-acetic acid p-tert-butyl cyclohexyl ester, and if the trans-isomer is mixed in the cis-acetic acid p-tert-butyl cyclohexyl ester, the fragrance of the cis-acetic acid p-tert-butyl cyclohexyl ester can be greatly reduced. Most of the cis/trans tert-butylcyclohexanol prepared by the existing reaction is a mixture of cis/trans tert-butylcyclohexanol, a mixture of cis/trans acetic acid and p-tert-butylcyclohexyl is further obtained after esterification, and the cis acetic acid and p-tert-butylcyclohexyl is extracted in a separation and purification mode, so that the operation is complex, and the product purity is influenced. Therefore, how to prepare the cis-tert-butylcyclohexanol with high selectivity in the reaction stage is related to the quality of the final product and the optimization of the production process.
Chinese patents CN1188098A and CN1264361A disclose a technical scheme for preparing cis-p-tert-butylcyclohexanol by hydrogenation in the presence of a rhodium catalyst and compounds such as hydrogen chloride, perchloric acid, anhydrous sulfuric acid and the like, but the process has the defects of complicated post-treatment, generation of a large amount of wastewater and the like. The progress of synthesis and separation research of cis-tert-butylcyclohexanol (Gaofengqin, applied chemical industry, 2014(10)) reports that a method for synthesizing high-content cis-tert-butylcyclohexanol by using Raney Ni, Pt/C, Pd/C, Rh/C and the like as catalysts is introduced, the effect is achieved by mainly controlling process conditions or adding hydrochloric acid into a system, but the addition of the hydrochloric acid requires that the grade of a pipe is sufficient, and a large amount of three wastes are generated in the post-treatment process, so that the industrial production is not facilitated.
Disclosure of Invention
The invention provides a hydrogenation catalyst and a preparation method thereof, the catalyst prepared by the method can stabilize an active component in an inner cavity of the catalyst through an organic ball cage carrier, and a target product is obtained with high selectivity when p-tert-butyl phenol is hydrogenated to prepare cis-p-tert-butyl cyclohexanol by utilizing the synergistic effect of the organic ball cage and the active component, and the catalyst has good catalytic activity. Therefore, the invention also provides an application of the hydrogenation catalyst in the preparation of cis-tert-butylcyclohexanol by hydrogenation of p-tert-butylphenol.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a hydrogenation catalyst comprises the following steps:
1) preparing a carrier: reacting tetra-aldehyde tetraphenylethylene with a diamine compound, and filtering to obtain an organic ball cage carrier; preferably, the molar ratio of the tetra-aldehyde tetraphenylethylene to the diamine compound is 1-5: 1; more preferably, the diamine compound is one or more of o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, isophoronediamine, diethylenetriamine and cyclohexanediamine;
2) preparing an active component: respectively preparing salt solutions of nano palladium and nano magnetic rhenium in the presence of a surfactant; the palladium salt can be one of palladium sulfate, palladium chloride, palladium nitrate, palladium carbonate and the like; the rhenium salt can be one of rhenium sulfate, rhenium chloride, rhenium nitrate, rhenium carbonate and the like;
3) mixing and refluxing the carrier and the active component prepared in the step 1) and the step 2) to obtain the hydrogenation catalyst; preferably, the mass ratio of the metal elements in the carrier and the active component is 20-100:1, and further, the mass ratio of the active component to the metal elements is 40-90% and the mass ratio of the nano magnetic rhenium is 10-60%.
Further, the step 1) is carried out under the conditions of protonic acid catalyst and no oxygen; the reaction solvent is organic solvent such as dioxane, tetrahydrofuran, acetonitrile, mesitylene, durene and the like.
Further, the addition amount of the protonic acid catalyst is 1 to 10 percent, preferably 5 percent of the mass of the raw materials;
more preferably, the protic acid catalyst is one or more of hydrochloric acid, acetic acid, sulfuric acid, citric acid and acetic anhydride.
Further, the reaction temperature of the step 1) is 80-150 ℃, and the reaction time is 50-100 h.
Further, in the step 1), after the reaction is completed, the reaction product is cooled to room temperature, and the product obtained by filtration is washed several times with anhydrous solvents such as tetrahydrofuran, and then filtered and dried to obtain the target product.
Further, the addition amount of the surfactant in the step 2) is 1-50 times of the mass of the palladium or rhenium element; preferably, the surfactant is one or more of alkyl polyglycoside, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and sodium dodecyl sulfonate.
Further, when preparing the active component salt solution in the step 2), firstly adding a dispersing agent to disperse the system, and then refluxing at 80-100 ℃ for 2-4h to obtain a suspension; preferably, the dispersant is one or more of nonpolar aliphatic hydrocarbon or aromatic hydrocarbon, polar solvent in ester or ketone, and alcohol polar solvent, and further preferably one or more of ethanol, isopropanol, acetone, cyclohexane, methanol, ethyl butyrate, ethyl acetate, cyclohexanol, butyl acetate, and acetonitrile.
Further, the step 3) adds NaHB at the same time when the carrier and the active component are mixed 4 Adjusting the size of the nano metal ions; preferably, the NaHB 4 The addition amount of (B) is 1-10% of the total mass of the carrier and the active component.
Further, the reflux temperature in the step 3) is 80-100 ℃, and the time is 1-4 h.
Further, the reaction solvent in step 3) may be dioxane, tetrahydrofuran, acetonitrile, mesitylene, durene, or other organic solvents.
The invention also provides a hydrogenation catalyst prepared by the method.
The invention also provides an application of the hydrogenation catalyst prepared by the method in preparation of cis-p-tert-butylcyclohexanol by hydrogenation of p-tert-butylphenol.
Further, the specific method for preparing cis-p-tert-butylcyclohexanol by hydrogenating p-tert-butylphenol comprises the following steps: adding a p-tert-butylphenol solution and a hydrogenation catalyst into an intermittent reaction kettle, reacting for 1-5h at 50-150 ℃, and recovering a product; preferably, the mass concentration of the p-tert-butyl phenol solution is 20-60%, and the addition amount of the hydrogenation catalyst is 1-3% of the total mass of the p-tert-butyl phenol solution. The reaction solvent can be common alcohol solvent such as ethanol, isopropanol, methanol, etc.
The invention has the following beneficial effects:
1) firstly synthesizes a three-dimensional organic ball cage carrier taking tetra-aldehyde tetraphenyl ethylene as a framework and Pd 2+ 、Re 2+ To effect coordination ofThe organic ball cage/nano particle compound can play a synergistic or tandem catalysis role in a reaction system for preparing cis-p-tert-butylcyclohexanol by hydrogenating p-tert-butylphenol, and not only has good catalytic activity, but also has high selectivity on a target product.
2) By means of NaHB 4 Regulating the size of nano metal ions in the active component, smaller Pd 2+ 、Re 2+ The catalyst shows higher catalytic activity in a p-tert-butyl phenol reaction system.
Drawings
FIG. 1 is a transmission electron micrograph of the organic cage carrier prepared in example 1.
FIG. 2 is a BET adsorption profile of the organic cage support of example 1.
FIG. 3 is a graph showing the distribution of pore sizes of the organic cage support in example 1.
FIG. 4 is an EDS elemental distribution plot of Pd and Re over the catalyst prepared in example 1.
Detailed Description
The invention is further illustrated by the accompanying drawings and specific examples, which are given by way of illustration only and do not limit the scope of the invention.
The main raw materials used in the examples of the present invention are as follows, and other raw materials are obtained from ordinary commercial sources unless otherwise specified.
Reagent Manufacturer of the product
Tetra-aldehyde tetraphenylethylene Henan alpha chemical industry
P-phenylenediamine Microphone forest
O-phenylenediamine Microphone forest
Palladium chloride Microphone forest
Rhenium chloride Microphone forest
Palladium acetate Aladdin chemical reagent
Alkyl polyglycosides Chemical engineering of Yousio
Hexadecyl trimethyl ammonium chloride Aladdin chemical reagent
Ethanol Chemical reagent for jujude
Acetic acid Tianjin Kemi Europe
Mesitylene Aladdin chemical reagent
P-tert-butylphenol Aladdin chemical reagent
The test instruments used in the examples were:
the gas phase was analyzed by using Shimadzu Angilent model 7820A gas chromatograph (hydrogen flame detector, nitrogen as carrier gas) and DB-5 capillary column (5% Phenyl Methyl Siloxan, 30 m.times.0.32 mm.times.0.25 μm), hydrogen flame detector (FID). The sample injector and detector temperatures were both 280 ℃; column temperature is controlled by adopting programmed temperature rise: the column temperature is initially kept at 100 ℃ for 0.5 minute, and the temperature is raised to 260 ℃ at 15 ℃/min and kept for 5 minutes. Column pressure 8.5868psi, flow rate 1.5 mL/min. Sample introduction amount: 0.2. mu.L. Conversion and selectivity were calculated using area normalization.
Scanning electron microscopy was performed using the MIRA3 v3LMH model.
N 2 The adsorption test adopts auxiliary matched equipment DES (X-ray energy spectrometer) of a scanning electron microscope (German Bruker QX200), and combines the scanning electron microscope to carry out qualitative and quantitative analysis on the element distribution of the selected area of the material within 2 minutes.
The pore structure was analyzed by an adsorption apparatus (Congta NOVA touch), the sample was degassed at 180 ℃ for 5 hours, the specific surface area was calculated by BET and t-plot methods, and the pore volume DFT theory was calculated.
[ example 1 ] A method for producing a polycarbonate
Weighing 8.88g of tetra-aldehyde tetraphenylethylene (0.02mol) and 1.08g of p-phenylenediamine (0.01mol), uniformly mixing, placing in a Parex glass container, adding 20ml of dioxane, and adding 2ml of 3mol/L acetic acid solution; the container was then frozen in liquid nitrogen, degassed three times, sealed and placed in a 120 ℃ oven for reaction for 72 h. After the reaction is finished, cooling to room temperature, filtering the solid, washing 3 times by using anhydrous tetrahydrofuran, centrifuging, filtering, and drying under vacuum conditions to obtain the organic ball cage carrier, wherein a transmission electron microscope image of the organic ball cage carrier is shown in figure 1. Carrying out N on the pore structure of the organic ball cage carrier 2 The adsorption test, BET curve and average pore size distribution are shown in fig. 2 and fig. 3, respectively.
Preparing an alkylpolyglycoside solution with the mass concentration of 0.6%, adding 20ml of alkylpolyglycoside solution into 5ml of 0.5% palladium acetate solution and 50g of absolute ethyl alcohol, refluxing for 4 hours at 80 ℃ to obtain a suspension, and centrifuging to collect solids; preparing a nano magnetic rhenium salt solution in the same way, and collecting the solid.
99g of organic ball cage and 1g of active component (palladium and rhenium in an element mass ratio of 1:1) were dissolvedIn 100ml of tetrahydrofuran, 1g of NaHB was then added 4 And refluxing for 2h at 80 ℃, filtering, washing, centrifuging, filtering again and drying the obtained solid to obtain a finished catalyst product. Warp of N 2 The average pore diameter of the catalyst was 7 angstroms by adsorption test. EDS analysis is respectively carried out on the finished catalyst product, the nano palladium and the nano magnetic rhenium, and the result is shown in figure 4, which shows that the nano palladium and the nano magnetic rhenium are successfully distributed in the carrier framework in the finished catalyst product.
[ example 2 ]
A hydrogenation catalyst was prepared according to the method of example 1, except for the amounts of feed added and the following options as shown in table 1: the diamine compound is o-phenylenediamine, and the protonic acid catalyst is 3mol/L hydrochloric acid solution. The catalyst has an average pore diameter of 5 angstroms.
[ example 3 ]
A hydrogenation catalyst was prepared according to the method of example 1, except for the amounts of feed added and the following options as shown in table 1: the diamine compound is m-phenylenediamine and the protonic acid catalyst is 0.5mol/L sulfuric acid solution. The average pore diameter of the catalyst is detected to be 8 angstroms.
[ example 4 ]
A hydrogenation catalyst was prepared according to the method of example 1, except for the amounts of feed added and the following options as shown in table 1: the diamine compound is isophorone diamine, and the protonic acid catalyst is 0.5mol/L citric acid solution. The catalyst has an average pore diameter of 3 angstroms.
[ example 5 ]
A hydrogenation catalyst was prepared according to the method of example 1, except for the amounts of feed added and the following options as shown in table 1: the diamine compound is cyclohexanediamine, and the protonic acid catalyst is 1mol/L acetic anhydride solution. The catalyst has an average pore diameter of 4 angstroms.
TABLE 1 raw material addition amount of each example
Figure BDA0002406802270000071
In order to verify the catalytic effect of the catalyst prepared by the method disclosed by the invention applied to the p-tert-butylphenol hydrogenation reaction, the catalysts prepared in the examples are respectively used for the following reactions:
400g of p-tert-butylphenol-isopropanol solution with the mass concentration of 60 percent and 12g of catalyst are added into a reaction kettle and reacted for 4 hours at the temperature of 100 ℃ under the pressure of 2 MPa. And after the reaction is finished, removing the solvent to obtain the target product cis-p-tert-butylcyclohexanol. The feedstock conversion and product selectivity of the catalysts in each example are shown in table 2:
TABLE 2 test of catalytic Performance of catalysts of the examples
Conversion rate/%) Cis body selectivity/%)
Example 1 99.99 88.3
Example 2 99.99 89.1
Example 3 99.99 87.3
Example 4 99.99 88.7
Example 5 99.99 89.8
In order to further show the beneficial effects of the technical scheme of the invention, referring to the method for preparing cis-tert-butylcyclohexanol by catalytic hydrogenation of p-tert-butylphenol, volume 32/2/2002 in fine chemical industry intermediates, p-tert-butylphenol is used as a starting material, Pd/C is used as a catalyst for catalytic action evaluation and is used as a comparative example of the invention, and the specific method comprises the following steps:
600g of 20 percent p-tert-butylphenol-ethanol solution and 12g of Pd/C catalyst are added into a reaction kettle, and the reaction is carried out for 5 hours at the temperature of 110 ℃ under the pressure of 3 MPa. And after the reaction is finished, removing ethanol to obtain cis-p-tert-butylcyclohexanol. The conversion rate of raw materials is more than 99.9 percent, and the selectivity of cis-form products is 76.2 percent.
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 additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.

Claims (16)

1. A preparation method of a hydrogenation catalyst is characterized by comprising the following steps:
1) preparing a carrier: reacting tetra-aldehyde tetraphenylethylene with a diamine compound, and filtering to obtain an organic ball cage carrier;
step 1) is carried out under the conditions of protonic acid catalyst and no oxygen; the diamine compound is one or more of o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, isophorone diamine, diethylenetriamine and cyclohexanediamine;
2) preparing an active component: respectively preparing salt solutions of nano palladium and nano rhenium in the presence of a surfactant;
the surfactant is one or more of alkyl polyglycoside, hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and dodecyl sodium sulfonate;
when the active component salt solution is prepared in the step 2), firstly, a dispersing agent is added to disperse the system, and then, the mixture is refluxed for 2 to 4 hours at the temperature of 80 to 100 ℃ to obtain a suspension;
3) mixing and refluxing the carrier and the active component prepared in the step 1) and the step 2) to obtain the hydrogenation catalyst;
the step 3) is that NaBH is added simultaneously when the carrier and the active component are mixed 4 The size of the nano metal ions is adjusted.
2. The method for preparing a hydrogenation catalyst according to claim 1, wherein the molar ratio of the tetraaldehyde tetraphenylethylene to the diamine compound in step 1) is 1-5: 1.
3. The method for preparing a hydrogenation catalyst according to claim 1, wherein in step 3), the mass ratio of the metal elements in the carrier and the active component is 20-100: 1.
4. The method for preparing a hydrogenation catalyst according to claim 3, wherein the active component comprises 40 to 90% by mass of nano-palladium and 10 to 60% by mass of nano-rhenium, based on the mass of the metal element.
5. The method for preparing a hydrogenation catalyst according to claim 1, wherein the protonic acid catalyst is added in an amount of 1 to 10% by mass based on the raw material in the step 1).
6. The method of claim 5, wherein the protonic acid catalyst is one or more of hydrochloric acid, acetic acid, sulfuric acid, citric acid and acetic anhydride.
7. The method for preparing a hydrogenation catalyst according to claim 5, wherein the reaction temperature in the step 1) is 80-150 ℃ and the reaction time is 50-100 h.
8. The method for preparing a hydrogenation catalyst according to any of claims 1 to 7, wherein the amount of the surfactant added in step 2) is 1 to 50 times the mass of the palladium or rhenium element.
9. The method for preparing a hydrogenation catalyst according to claim 8, wherein in the step 2), the dispersant is one or more of a nonpolar aliphatic hydrocarbon or aromatic hydrocarbon, a polar solvent in an ester or ketone, and a polar solvent in an alcohol.
10. The method for preparing a hydrogenation catalyst according to claim 9, wherein the dispersant is one or more selected from the group consisting of ethanol, isopropanol, acetone, cyclohexane, methanol, ethyl butyrate, ethyl acetate, cyclohexanol, butyl acetate and acetonitrile in the step 2).
11. The method of any of claims 1-7, wherein in step 3), the NaBH is added 4 The addition amount of (B) is 1-10% of the total mass of the carrier and the active component.
12. The method for preparing a hydrogenation catalyst according to claim 11, wherein the reflux temperature in step 3) is 80-100 ℃ and the time is 1-4 h.
13. A hydrogenation catalyst prepared according to the process of any one of claims 1 to 12.
14. Use of a hydrogenation catalyst as prepared by a process as defined in any one of claims 1 to 12 or a hydrogenation catalyst as defined in claim 13 for the hydrogenation of p-tert-butylphenol to produce cis-p-tert-butylcyclohexanol.
15. The use according to claim 14, wherein the hydrogenation of p-tert-butylphenol to produce cis-p-tert-butylcyclohexanol is carried out by: adding p-tert-butylphenol solution and hydrogenation catalyst into a batch reactor, reacting for 1-5h at 50-150 ℃, and recovering the product.
16. The use of claim 15, wherein the mass concentration of the p-tert-butylphenol solution is 20 to 60%, and the amount of the hydrogenation catalyst added is 1 to 3% of the total mass of the p-tert-butylphenol solution.
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CN104744216A (en) * 2015-03-24 2015-07-01 万华化学集团股份有限公司 Method for preparing beta-phenethyl alcohol
CN107827712A (en) * 2017-10-31 2018-03-23 安徽华业香料合肥有限公司 A kind of production method of verdox synthetic perfume
CN110229333A (en) * 2019-06-25 2019-09-13 湘潭大学 A kind of synthetic method of new type polyimide
CN110743546A (en) * 2019-10-31 2020-02-04 西安凯立新材料股份有限公司 Catalyst for continuously preparing cis-p-tert-butylcyclohexanol, preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1190091A (en) * 1996-12-09 1998-08-12 巴斯福股份公司 Hydrogenation of aromatic compound in presence of supported catalyst
JP2004331746A (en) * 2003-05-02 2004-11-25 National Institute Of Advanced Industrial & Technology Method for producing polycarbonate
CN104368358A (en) * 2014-10-11 2015-02-25 中国科学院青岛生物能源与过程研究所 Catalyst applicable to succinic acid hydrogenation reaction, and preparation method and hydrogenation reaction method thereof
CN104744216A (en) * 2015-03-24 2015-07-01 万华化学集团股份有限公司 Method for preparing beta-phenethyl alcohol
CN107827712A (en) * 2017-10-31 2018-03-23 安徽华业香料合肥有限公司 A kind of production method of verdox synthetic perfume
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