CN112778083B - Method for synthesizing cyclohexanol by 2, 6-dimethoxyphenol - Google Patents

Method for synthesizing cyclohexanol by 2, 6-dimethoxyphenol Download PDF

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CN112778083B
CN112778083B CN202011638784.2A CN202011638784A CN112778083B CN 112778083 B CN112778083 B CN 112778083B CN 202011638784 A CN202011638784 A CN 202011638784A CN 112778083 B CN112778083 B CN 112778083B
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dimethoxyphenol
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cyclohexanol
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毛璟博
周锦霞
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Dalian University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to the field of organic synthesis, and discloses a method for synthesizing cyclohexanol by using 2, 6-dimethoxyphenol. The invention uses Pt/Co for the first time 3 O 4 The catalyst is used for carrying out hydrodeoxygenation treatment on the 2, 6-dimethoxyphenol to realize the synthesis of the final product cyclohexanol. The method provided by the invention has single product and uses Pt/Co 3 O 4 The catalyst makes the cyclohexanol selectivity in the final reaction product over 95%. The reaction temperature is controlled between 373K and 873K, and 2, 6-dimethoxyphenol can quickly realize complete conversion. Pt/Co of the invention 3 O 4 The catalyst has better reusability in the intermittent kettle reaction and can run on a fixed bed for a long time.

Description

Method for synthesizing cyclohexanol by 2, 6-dimethoxyphenol
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing a final product cyclohexanol by using 2, 6-dimethoxyphenol.
Background
Cyclohexanol is an important chemical and drug synthesis intermediate, and the research of obtaining corresponding saturated alcohol alkane compounds through continuous hydrogenation of aromatic phenol compounds has been paid much attention in the world industrial industry. Phase transfer catalysis or homogeneous catalysis can realize the important process, and heterogeneous catalysts are widely applied to the field of hydrogenation due to convenient separation and easy regeneration.
2, 6-dimethoxy phenol is also called syringol, and is a structural monomer formed after cracking lignin. Because the syringol can be obtained by biotransformation, the syringol has large content and wide range in the nature, can replace petroleum, and can be used as a biofuel or a chemical production raw material. At present, guaiacol and phenol are generally used as lignin model compounds to study the hydrogenation performance, for example, on sulfurized CoMo and CoMo catalysts, guaiacol can catalyze hydrogenation to generate benzene, cyclohexene and cyclohexane, and the yield of hydrocarbon can reach 72.2% when the reaction is carried out at 325 DEG C [1] . Syringol is more difficult to react than guaiacol and phenol due to the large steric hindrance [2] And simultaneously, because the compound has two ortho methoxyl groups, the carbon is easier to deposit [3] . Riyang et al use Ni/SiO 2 -Al 2 O 3 Catalyzing 2, 6-dimethoxyphenol, the conversion rate of raw materials is about 95 percent at 200 ℃, the selectivity of cyclohexane is about 97 percent, and Al in the catalyst 2 O 3 The provision of an acid center is key to the reaction which can take place [4] 。
At present, co is used 3 O 4 Or Pt/Co 3 O 4 The catalytic reaction of 2, 6-dimethoxyphenol hydrodeoxygenation carried out as a catalyst is not reported.
[1]J.B.Bredenberg,M.Huuska,P.Toropainen,J.Catal.120(1989)401–408.
[2]A.Sequeiros,L.Serrano,J.Labidi,J.Chem.Technol.Biotechnol.91(2016)1809–1815.
[3]M.Asmadi,H.Kawamoto,S.Saka,J.Anal.Appl.Pyrolysis 92(2011)88–98.
[4]R.Shu,Y.Xu,L.Ma,Q.Zhang,P.Chen,T.Wang.Catalysis CommuCocations 91(2017)1–5.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention uses Co for the first time 3 O 4 Or Pt/Co 3 O 4 The catalyst is used for carrying out hydrodeoxygenation treatment on the 2, 6-dimethoxyphenol to realize the synthesis of the final product cyclohexanol. The method provided by the invention has single product and high selectivity close to 100%.
In order to achieve the purpose, the invention adopts the following technical scheme that the method for synthesizing cyclohexanol by 2, 6-dimethoxyphenol specifically comprises the following steps: dispersing 2, 6-dimethoxyphenol in an organic solvent to obtain a reaction solution, and adding Co 3 O 4 Or Pt/Co 3 O 4 Adding a catalyst into the reaction liquid, sealing, removing oxygen by using nitrogen replacement, finally introducing hydrogen with the pressure not more than 30MPa, reacting at 373-873K for 1-12 h to obtain cyclohexanol;
the Co 3 O 4 Or Pt/Co 3 O 4 The dosage of the catalyst is 0.1 to 40 percent of the mass of the 2, 6-dimethoxy phenol;
the organic solvent is: any one of benzene, toluene, n-decane, n-tetradecane, or n-hexadecane.
Further, the Pt/Co 3 O 4 The catalyst can be prepared by a coprecipitation method or an equivalent-volume impregnation method; wherein the loading amount of Pt is Pt/Co 3 O 4 0.001wt% -10 wt% of the total mass of the catalyst.
Further, the Pt-containing compound includes: at least one of chloroplatinic acid, platinum bromide, platinum iodide, potassium chloroplatinate, ammonium hexachloroplatinate, potassium hexachloroplatinate, platinum nitrate, tetraammine platinum nitrate, potassium tetrachloroplatinate, sodium tetrachloroplatinate, platinum acetylacetonate or nano-platinum particles; the Co-containing compound includes: cobalt nitrate, cobalt chloride, cobalt bromide, cobalt sulfate, perchloro-cobaltic acid, cobalt ammonium sulfate, cobalt acetylacetonate and cobalt sulfide.
Co preparation by coprecipitation method 3 O 4 Or Pt/Co 3 O 4 The specific method of the catalyst comprises the following steps: dissolving a Pt-containing compound and a cobalt-containing compound into water according to the molar ratio of Pt to Co, wherein the concentration of the Pt and Co compounds is between 0.001mol/L and 5mol/L, dropwise adding the obtained solution into a sodium hydroxide aqueous solution (0.05 mol/L to 5 mol/L), stirring the mixture at room temperature to 423K for 1min to 72h, filtering, washing to neutrality, drying at 273K to 473K for 1min to 72h, and roasting at 273K to 773K for 1min to 10h.
Pt/Co preparation by adopting equal-volume impregnation method 3 O 4 The specific method of the catalyst comprises the following steps: dissolving Pt-containing compound with the concentration of 0.0001-50 wt% in any one of liquid solvents such as water, formic acid, acetic acid, propionic acid, methanol and the like to prepare Pt solution, and then according to the mass ratio of Pt to Co, 0.0001-10 wt% of Co 3 O 4 Adding the mixture into Pt solution, standing or stirring for 1 min-72 h, drying for 1 min-72 h at 273K-473K, and roasting for 1 min-10 h at 273K-773K. Co used 3 O 4 Is commercial Co 3 O 4 Or a sample obtained by dripping Co salt solution into sodium hydroxide solution to obtain a precipitate, filtering, washing and roasting.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses Co 3 O 4 Or Pt/Co 3 O 4 The catalyst makes the cyclohexanol selectivity in the final reaction product near 100%. The reaction temperature is controlled between 373K and 873K, and the 2, 6-dimethoxyphenol can be quickly and completely converted. Co of the invention 3 O 4 Or Pt/Co 3 O 4 Catalyst inThe repeated use performance in the intermittent kettle reaction is better, and the intermittent kettle can run on a fixed bed for a long time.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise stated, the experimental methods adopted by the invention are all conventional methods, and the experimental equipment, materials, reagents and the like used in the method can be purchased from chemical companies.
The content of platinum in the Pt catalyst can be measured by ICP or XRF, and the better effect can be obtained when the Pt loading amount in the Pt catalyst is within 0.001-10 wt.%. Firstly, pt/Co 3 O 4 The catalyst is roasted in a muffle furnace, so that gold can be effectively attached to the surface of the carrier. A certain amount of Pt/Co 3 O 4 Adding the catalyst into the reactant solution, sealing, replacing to remove oxygen, and finally introducing hydrogen (within 30 MPa) with certain pressure. Controlling the temperature of the reactor between 373K and 873K, sampling after a period of reaction, and calculating the conversion rate of the raw materials and the yield of each product.
Figure GDA0003832847110000041
Figure GDA0003832847110000042
n 0 : the molar amount (mol) of 2, 6-dimethoxyphenol in the reaction raw material;
n 1 : the molar amount (mol) of 2, 6-dimethoxyphenol in the reaction solution after the completion of the reaction.
n 2 : molar amount (mol) of cyclohexanol.
Example 1
Preparation of Co by deposition precipitation method 3 O 4 Or Pt/Co 3 O 4 Catalyst: preparing a solution with the cobalt nitrate concentration of 0.5mol/L and the platinum chloride concentration of 0.005mol/L, dropwise adding the solution into a 1mol/L NaOH solution under the stirring state, stirring the solution at room temperature for 2 hours, filtering the solution, and washing a filter cake by using deionized water until the filter cake is finishedThe filtrate was neutral. And drying the filter cake for 12 hours at 380K, finally roasting the catalyst for 2 hours at 623K in a muffle furnace, drying and sealing for later use.
0.05g of the catalyst was placed in a batch autoclave reactor, to which was then added 0.50g of 2, 6-dimethoxyphenol and 10ml of n-decane. The reaction kettle is sealed, nitrogen is used for purging for 3 times, and then 3.0MPa hydrogen is introduced. The reaction kettle was warmed to 573K and the reaction was continued for 2h at a stirring rate of 700 rpm.
Example 2
The reaction time was 4 hours, and the catalyst preparation method, the amount of the feed and the reaction conditions were substantially the same as in example 1.
Example 3
The reaction temperature was 623K, and the catalyst preparation method, the amount of the feed and the reaction conditions were substantially the same as those in example 1.
The reaction results of examples 1 to 3 are shown in Table 1.
TABLE 1 summary of the reaction results of examples 1-3
Figure GDA0003832847110000051
Example 4
The concentration of cobalt nitrate in the metal salt solution was 0.5mol/L, chloroplatinic acid was not contained, and the preparation method, the amount of the feed and the reaction conditions of the catalyst were substantially the same as those in example 1.
Example 5
The concentration of cobalt nitrate in the metal salt solution was 0.4mol/L, the concentration of chloroplatinic acid was 0.02%, and the preparation method, the amount of the feed and the reaction conditions of the catalyst were substantially the same as those in example 1.
The reaction results of examples 4 and 5 are shown in Table 2.
TABLE 2 summary of the reaction results of examples 4 and 5
Figure GDA0003832847110000052
Example 6
1.0g of 2, 6-dimethoxyphenol was contained in the reaction raw material, and the preparation method, the amount of the charged material and the reaction conditions of the catalyst were the same as those of example 1.
Example 7
The amount of the catalyst used in the reaction materials was 0.1g, and the preparation method, the amount of the catalyst charged and the reaction conditions were substantially the same as those in example 1.
Example 8
The reaction temperature was 523K, and the catalyst preparation method, the amount of feed and the reaction conditions were substantially the same as in example 1.
Example 9
The reaction temperature is 623K, the reaction time is 3h, and the preparation method, the feeding amount and the reaction conditions of the catalyst are basically the same as those of the example 1.
The reaction results of examples 6, 7, 8 and 9 are shown in Table 3.
TABLE 3 results of the reactions of examples 6 to 9
Figure GDA0003832847110000061
As can be seen from the data in tables 1 to 3, co was used 3 O 4 Or Pt/Co 3 O 4 The catalyst can convert 2, 6-dimethoxy phenol into cyclohexanol with high efficiency, single kind of final product and basically saturated benzene ring. The reaction rate is improved by increasing the temperature, 2, 6-dimethoxyphenol is basically completely converted after 623K reaction for 3 hours, the selectivity of cyclohexanol is over 95 percent, and meanwhile, the introduction of Pt can effectively improve Co by comparing examples 1 and 4 3 O 4 Catalytic performance on 2, 6-dimethoxyphenol.
The above description is only for the purpose of creating a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.

Claims (1)

1. A method for synthesizing cyclohexanol by 2, 6-dimethoxy phenol is characterized in thatPreparation of Co by deposition precipitation 3 O 4 Or Pt/Co 3 O 4 Catalyst: preparing a solution with the concentration of cobalt nitrate of 0.5mol/L and the concentration of platinum chloride of 0.005mol/L, dropwise adding the solution into a 1mol/L NaOH solution under the stirring state, stirring the solution at room temperature for 2 hours, filtering the solution, and washing a filter cake by using deionized water until the filtrate is neutral; drying the filter cake for 12 hours at 380K, finally roasting the catalyst for 2 hours in a muffle furnace at 623K, drying and sealing for later use;
putting 0.05g of catalyst into a high-pressure batch kettle reactor, and then adding 0.50g of 2, 6-dimethoxyphenol and 10ml of n-decane into the high-pressure batch kettle reactor; sealing the reaction kettle, purging for 3 times by using nitrogen, and introducing 3.0MPa hydrogen; the reaction kettle is heated to 623K, and the reaction is continued for 3h at the stirring speed of 700 rpm.
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