A phenolic compound hydrodeoxygenation catalyst, a preparation method and application thereof

Abstract

The application discloses a phenolic compound hydrodeoxygenation catalyst and a preparation method and application thereof, and belongs to the field of biomass conversion and coal-based liquid fuel. The catalyst is a supported catalyst, and comprises an active support and a carrier. The carrier is foamed nickel, and the active support is a composite of flocculent CoB nanomaterial and thin sheet copper cobalt hydroxide. The preparation process comprises the following steps: firstly, depositing polyaniline on the foamed nickel by using an electrochemical deposition method; then, depositing Co(OH)F on the foamed nickel by using the surface modification effect of the polyaniline; preparing a foamed nickel / Co-B composite by using reduction boronization; and finally, depositing copper cobalt hydroxide on the surface of the foamed nickel / Co-B composite to obtain the phenolic compound hydrodeoxygenation catalyst. The catalyst has high catalytic activity and high selectivity in the phenolic compound hydrodeoxygenation reaction, and has a good application prospect in the fields of biomass conversion and coal-based liquid fuel.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of catalyst and its preparation and application, specifically to a kind of phenolic compound hydrogenolysis catalyst and its preparation method and application. BACKGROUND

[0002] The development of society cannot be separated from the support of energy, and traditional fossil energy is gradually exhausted, and the increasingly serious environmental problems also force mankind to constantly seek new renewable resources. In the process of processing and utilization of oil, coal-based liquid fuel and oil obtained by lignin conversion, deoxygenation is needed, and the deoxygenation hydrogenation of phenolic compounds is a key step.

[0003] Chinese patent CN112844466A discloses a kind of green biomass charcoal modified molecular sieve supported metal catalyst and its preparation method and application. The preparation method of the catalyst includes the following steps: (1) adding biomass charcoal and molecular sieve into a mixed solvent of ethanol and water, mixing to obtain a mixed solution; wherein the biomass charcoal is at least one of pine nut shell biomass charcoal, rice husk biomass charcoal, eucalyptus sawdust biomass charcoal and chlorella biomass charcoal; (2) adding nickel salt and vanadium salt into the mixed solution, uniformly aging after standing, drying to obtain a catalyst precursor; (3) grinding and sieving the catalyst precursor, and then reducing under a reducing gas atmosphere to obtain a green biomass charcoal modified molecular sieve supported metal catalyst.

[0004] Chinese patent CN110935473A provides a kind of hydrogenolysis catalyst and its preparation method and application. The hydrogenolysis catalyst includes active components and carrier, and nickel and molybdenum are used as active components, and sulfuric acid hydrogen salt modified γ-Al2O3 is used as carrier. The hydrogenolysis catalyst is used as a reaction catalyst to treat the hydrogenolysis reaction of oil-soluble phase of bio-oil. By surface modification of the catalyst, the ability of the catalyst to adsorb oxygen-containing functional groups in phenolic compounds is improved, so as to achieve the purpose of high selectivity of catalytic phenolic compounds to prepare hydrocarbon substances.

[0005] However, the phenolic compound hydrogenolysis catalyst prepared by these methods has some shortcomings. For molecular sieve carriers, phenolic compounds are often significantly diffusion limited and need to pass through long micropore diffusion channels to contact metal active centers, resulting in reduced catalytic activity. Although sulfide catalysts have high aromatic selectivity, the preparation process requires presulfidation, which is complex in actual operation; in addition, sulfides have greater environmental pollution. SUMMARY

[0006] The purpose of the present application is to improve the reaction performance of the catalyst in the phenolic compound hydrogenolysis reaction, and the present application provides a kind of phenolic compound hydrogenolysis catalyst and its preparation method.

[0007] Technical solution: The phenolic compound hydrodeoxygenation catalyst provided by the present application is a supported catalyst, which comprises an active support and a carrier; wherein the carrier is foamed nickel, and the active support is a composite of flocculent CoB nanomaterial and flaky copper cobalt hydroxide. The flaky copper cobalt hydroxide is deposited on the foamed nickel with flocculent CoB attached to the surface, thereby forming the phenolic compound hydrodeoxygenation catalyst.

[0008] The preparation method of the phenolic compound hydrodeoxygenation catalyst comprises the following steps:

[0009] The preparation method of the phenolic compound hydrodeoxygenation catalyst comprises the following steps:

[0010] (1) The foamed nickel is cleaned and dried to obtain clean foamed nickel; a dilute sulfuric acid solution with a mass fraction of 0.2% to 2% is prepared, aniline is added according to a mass ratio of aniline to the dilute sulfuric acid solution of 0.05:1 to 0.1:1, and the mixture is stirred uniformly to obtain an electrolyte; the clean foamed nickel is cut according to a mass ratio of aniline to the clean foamed nickel of 0.5:1 to 2:1, and the clean foamed nickel is clamped by a purple copper electrode clamp as a working electrode, Ag / AgCl is used as a reference electrode, and a platinum sheet is used as a counter electrode, and the reaction is carried out at a constant potential of 0.8 to 1.2 V for 5 to 40 min, thereby obtaining polyaniline modified foamed nickel.

[0011] (2) A cobalt salt aqueous solution with a mass fraction of 0.1% to 2% is prepared, an organic base is added according to a mass ratio of the organic base to the cobalt salt aqueous solution of 0.02:1 to 0.1:1, a fluoride is added according to a mass ratio of the fluoride to the cobalt salt aqueous solution of 0.01:1 to 0.05:1, and the mixture is stirred for 2 to 6 h, and then is transferred to a pressure-resistant sealed container; the polyaniline modified foamed nickel obtained in step (1) is suspended in the reaction solution according to a mass ratio of the polyaniline modified foamed nickel to the cobalt salt aqueous solution of 0.01:1 to 0.05:1, and the reaction is carried out at 100 to 150 ℃ for 8 to 12 h; centrifugation is performed, and the polyaniline modified foamed nickel is washed with water in an amount of 50 to 200 times the mass of the polyaniline modified foamed nickel, and is dried at 60 to 90 ℃ for 6 to 12 h, thereby obtaining polyaniline modified foamed nickel / Co(OH)F. Preferably, the water washing is deionized water washing.

[0012] (3) configuring a mass fraction of 0.2% to 5% of sodium hydroxide aqueous solution, adding sodium borohydride according to a mass ratio of sodium borohydride to sodium hydroxide aqueous solution of 0.01 to 0.1:1 to obtain sodium borohydride aqueous solution, configuring a mass fraction of 2% to 10% of cobalt chloride aqueous solution, and repeatedly immersing the polyaniline modified foam nickel / Co(OH)F obtained in step (2) in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution for 5 to 20 seconds, respectively, for 20 to 50 times, drying at 60 to 90℃ for 6 to 12 hours, transferring into a heating device, passing in inert gas, heating to 300 to 500℃, and calcining for 2 to 5 hours to obtain a foam nickel / Co-B composite.

[0013] (4) configuring a water solution containing copper salt and cobalt salt according to a mass ratio of copper salt, cobalt salt and water of 0.001 to 0.02:0.001 to 0.02:1, adding basic substance according to a mass ratio of basic substance to copper salt of 0.2:1 to 2:1, stirring for 1 to 4 hours, transferring into a pressure-tight container, suspending the foam nickel / Co-B composite in the reaction solution according to a mass ratio of foam nickel / Co-B composite to copper salt of 5:1 to 20:1, reacting at 80 to 150℃ for 8 to 12 hours, centrifuging, washing with water of 50 to 200 times the mass of the foam nickel / Co-B composite, and drying at 60 to 90℃ for 6 to 12 hours to obtain a phenolic compound hydrogenation and deoxidation catalyst. Preferably, the water washing is deionized water washing.

[0014] The preparation method of the phenolic compound hydrogenation and deoxidation catalyst, and the cleaning, drying of the foam nickel in step (1) to obtain clean foam nickel is specifically as follows: cleaning the foam nickel with hydrochloric acid, acetone, ethanol and water in sequence, and drying at 80 to 100℃ for 6 to 12 hours to obtain clean foam nickel.

[0015] The preparation method of the phenolic compound hydrogenation and deoxidation catalyst, and the cobalt salt in step (2) is one of cobalt nitrate hexahydrate and cobalt chloride hexahydrate, the organic base is one of urea, thiourea and sodium carboxylate, and the fluoride is one of ammonium fluoride, sodium fluoride and lithium fluoride.

[0016] The preparation method of the phenolic compound hydrogenation and deoxidation catalyst, and the pressure-tight container in step (2) and step (4) is a reaction kettle.

[0017] The preparation method of the phenolic compound hydrogenation and deoxidation catalyst, and the heating device in step (3) is a tube furnace.

[0018] The preparation method of the phenolic compound hydrogenation and deoxidation catalyst, and the inert gas in step (3) is nitrogen or argon.

[0019] The preparation method of the phenolic compound hydrodeoxygenation catalyst, the copper salt in step (4) is one of copper sulfate, copper nitrate and copper chloride, the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate, and the basic substance is one of sodium hydroxide, potassium hydroxide and urea.

[0020] The phenolic compound hydrodeoxygenation catalyst is applied to a phenolic compound hydrodeoxygenation reaction.

[0021] Advantages: compared with the prior art, the advantages of the present application are: (1) the polyaniline modified foam nickel can improve the surface properties of the foam nickel, is conducive to the uniform deposition of the flocculent CoB nanomaterial on the foam nickel, improves the uniformity of the active components of the catalyst, and improves the electron transfer capacity between the foam nickel and the flocculent CoB nanomaterial through the polyaniline, and improves the synergistic effect between the catalyst components. (2) The flocculent CoB nanomaterial is deposited with thin sheet copper cobalt hydroxide by using the coprecipitation method, and the thin sheet copper cobalt hydroxide is vertically grown on the surface of the CoB nanomaterial, which can greatly reduce the mass transfer resistance between the reactants and the catalyst components, and improve the catalytic activity of the catalyst. (3) In the prepared catalyst, the good C-O bond activation ability of the copper cobalt hydroxide, the excellent hydrogenation reduction ability of the CoB nanomaterial and the foam nickel, and the porous adsorption characteristics of the foam nickel are combined, which is helpful to the combination of the catalytic effects between the catalyst components, and improves the reaction performance of the catalyst in the phenolic compound hydrodeoxygenation reaction. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The phenolic compound hydrodeoxygenation catalyst prepared in Example 1. DETAILED DESCRIPTION

[0023] The present application will be further described below in combination with specific examples.

[0024] Example 1

[0025] (1) The foam nickel is sequentially cleaned with hydrochloric acid, acetone, ethanol and water, dried at 85℃ for 10h to obtain clean foam nickel; a dilute sulfuric acid solution with a mass fraction of 1.0% is prepared, aniline is added according to the mass ratio of aniline to dilute sulfuric acid solution 0.07:1, and stirred uniformly to obtain an electrolyte, and the clean foam nickel is cut according to the mass ratio of aniline to clean foam nickel 0.8:1, and the clean foam nickel is clamped with a copper electrode clamp as a working electrode, Ag / AgCl as a reference electrode, and a platinum sheet as a counter electrode, and reacted at a constant potential of 1V for 40min to obtain polyaniline modified foam nickel.

[0026] (2) The mass fraction of the prepared cobalt nitrate hexahydrate aqueous solution was 1.2%, and then urea was added according to the mass ratio of urea to cobalt nitrate hexahydrate aqueous solution of 0.08:1, sodium fluoride was added according to the mass ratio of sodium fluoride to cobalt nitrate hexahydrate aqueous solution of 0.04:1, and stirring was performed for 6 h. Then, the reaction solution was transferred into a reaction kettle, polyaniline modified foam nickel was suspended in the reaction solution according to the mass ratio of polyaniline modified foam nickel to cobalt nitrate hexahydrate aqueous solution of 0.03:1, and reaction was performed at 105°C for 11 h. After centrifugation, the polyaniline modified foam nickel was washed with deionized water in an amount of 80 times the mass of the polyaniline modified foam nickel, and then dried at 60°C for 12 h to obtain polyaniline modified foam nickel / Co(OH)F.

[0027] (3) The mass fraction of the prepared sodium borohydride aqueous solution was 0.2%, and then sodium borohydride was added according to the mass ratio of sodium borohydride to sodium hydroxide aqueous solution of 0.09:1 to obtain the sodium borohydride aqueous solution. The polyaniline modified foam nickel / Co(OH)F was repeatedly immersed in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution for 9 s, and the repeated number was 40. Then, the polyaniline modified foam nickel / Co(OH)F was dried at 60°C for 11 h, transferred into a tube furnace, and then nitrogen was introduced. The temperature was increased to 380°C, and then the polyaniline modified foam nickel / Co(OH)F was calcined for 4 h to obtain a foam nickel / Co-B composite.

[0028] (4) The mass ratio of copper sulfate, cobalt chloride hexahydrate and deionized water was 0.018:0.003:1 to prepare an aqueous solution containing copper sulfate and cobalt chloride hexahydrate. Sodium hydroxide was added according to the mass ratio of sodium hydroxide to copper sulfate of 0.2:1, and stirring was performed for 2 h. Then, the reaction solution was transferred into a reaction kettle, and then the foam nickel / Co-B composite was suspended in the reaction solution according to the mass ratio of the foam nickel / Co-B composite to copper sulfate of 9:1. Reaction was performed at 120°C for 9 h. After centrifugation, the foam nickel / Co-B composite was washed with deionized water in an amount of 165 times the mass of the foam nickel / Co-B composite, and then dried at 75°C for 8 h to obtain a phenolic compound hydrodeoxygenation catalyst. The prepared phenolic compound hydrodeoxygenation catalyst was detected in a scanning electron microscope, and the results are shown in FIG. 2. Figure 1

[0029] The catalyst was applied to a phenol hydrodeoxygenation reaction, the solvent was n-dodecane, the reaction temperature was 230°C, the reaction pressure was 2 MPa, and the reaction time was 4 h. The conversion rate of phenol was 95%, and the main product was cyclohexane. The selectivity of cyclohexane was 96%.

[0030] Example 2

[0031] ​The nickel foam is cleaned with hydrochloric acid, acetone, ethanol and water in sequence, dried at 100℃ for 6h to obtain clean nickel foam; a dilute sulfuric acid solution with a mass fraction of 1.3% is prepared, aniline is added according to a mass ratio of aniline to the dilute sulfuric acid solution of 0.05:1, and stirred uniformly to obtain an electrolyte, the clean nickel foam is cut according to a mass ratio of aniline to clean nickel foam of 0.5:1, the clean nickel foam is clamped as a working electrode with a red copper electrode clamp, Ag / AgCl is used as a reference electrode, and a platinum plate is used as a counter electrode, and the reaction is carried out at a constant potential of 0.8V for 20min to obtain polyaniline modified nickel foam.

[0032] A cobalt chloride hexahydrate aqueous solution with a mass fraction of 0.9% is prepared, urea is added according to a mass ratio of urea to the cobalt chloride hexahydrate aqueous solution of 0.02:1, ammonium fluoride is added according to a mass ratio of ammonium fluoride to the cobalt chloride hexahydrate aqueous solution of 0.01:1, stirred for 3h, transferred into a reaction kettle, and the polyaniline modified nickel foam is suspended in the reaction solution according to a mass ratio of the polyaniline modified nickel foam to the cobalt chloride hexahydrate aqueous solution of 0.02:1, and the reaction is carried out at 120℃ for 10h, centrifuged, washed with deionized water with a volume of 150 times the mass of the polyaniline modified nickel foam, and dried at 80℃ for 8h to obtain polyaniline modified nickel foam / Co(OH)F.

[0033] A sodium hydroxide aqueous solution with a mass fraction of 2% is prepared, sodium borohydride is added according to a mass ratio of sodium borohydride to the sodium hydroxide aqueous solution of 0.07:1 to obtain a sodium borohydride aqueous solution, a cobalt chloride aqueous solution with a mass fraction of 3% is prepared, and the polyaniline modified nickel foam / Co(OH)F is repeatedly immersed in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution in sequence for 12s, the number of repetitions is 30 times, dried at 80℃ for 10h, transferred into a tube furnace, argon is introduced, heated to 300℃, and calcined for 4.5h to obtain nickel foam / Co-B composite.

[0034] A water solution containing copper sulfate and cobalt chloride hexahydrate is prepared according to a mass ratio of copper nitrate, cobalt chloride hexahydrate and deionized water of 0.013:0.007:1, potassium hydroxide is added according to a mass ratio of potassium hydroxide to copper sulfate of 1.7:1, stirred for 3h, transferred into a reaction kettle, and the nickel foam / Co-B composite is suspended in the reaction solution according to a mass ratio of the nickel foam / Co-B composite to copper sulfate of 12:1, the reaction is carried out at 130℃ for 8.5h, centrifuged, washed with deionized water with a volume of 120 times the mass of the nickel foam / Co-B composite, and dried at 85℃ for 7h to obtain a phenolic compound hydrogenation deoxygenation catalyst.

[0035] The prepared CoB nanomaterial is in flocculent structure, and the copper cobalt hydroxide composite is in flaky structure. The catalyst is applied to the hydrodeoxygenation reaction of phenol, the solvent is n-tetradecane, the reaction temperature is 230 DEG C, the reaction pressure is 2 MPa, the reaction time is 4 h, the conversion rate of phenol is 92%, and the main product is cyclohexane, and the selectivity of cyclohexane is 99%.

[0036] Example 3

[0037] The foam nickel is sequentially cleaned with hydrochloric acid, acetone, ethanol and water, and dried at 95 DEG C for 9 h to obtain clean foam nickel; a 2% mass fraction dilute sulfuric acid solution is prepared, aniline is added according to the mass ratio of aniline to dilute sulfuric acid solution 0.06:1, and stirred to obtain an electrolyte, and the clean foam nickel is cut according to the mass ratio of aniline to clean foam nickel 1.3:1, the clean foam nickel is clamped as a working electrode with a red copper electrode clamp, Ag / AgCl is used as a reference electrode, and a platinum plate is used as a counter electrode, and the reaction is carried out at a constant potential of 0.9 V for 35 min to obtain polyaniline modified foam nickel.

[0038] A 0.6% mass fraction cobalt chloride hexahydrate aqueous solution is prepared, thiourea is added according to the mass ratio of thiourea to cobalt chloride hexahydrate aqueous solution 0.1:1, ammonium fluoride is added according to the mass ratio of ammonium fluoride to cobalt chloride hexahydrate aqueous solution 0.04:1, and stirred for 4 h, and then transferred to a reaction kettle, the polyaniline modified foam nickel is suspended in the reaction solution according to the mass ratio of polyaniline modified foam nickel to cobalt chloride hexahydrate aqueous solution 0.04:1, and the reaction is carried out at 110 DEG C for 12 h, centrifuged, washed with deionized water 50 times the mass of the polyaniline modified foam nickel, and dried at 70 DEG C for 11 h to obtain polyaniline modified foam nickel / Co(OH)F.

[0039] A 1% mass fraction sodium hydroxide aqueous solution is prepared, sodium borohydride is added according to the mass ratio of sodium borohydride to sodium hydroxide aqueous solution 0.04:1 to obtain a sodium borohydride aqueous solution, a 5% mass fraction cobalt chloride aqueous solution is prepared, and the polyaniline modified foam nickel / Co(OH)F is sequentially immersed in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution for 18 s, the number of repetitions is 20 times, and the polyaniline modified foam nickel / Co(OH)F is dried at 85 DEG C for 7 h, transferred to a tube furnace, argon is introduced, heated to 330 DEG C, and calcined for 5 h to obtain foam nickel / Co-B composite.

[0040] The phenolic compound hydrogenation deoxidization catalyst was prepared by the following steps: preparing an aqueous solution containing cupric chloride and cobalt chloride hexahydrate according to the mass ratio of cupric chloride, cobalt chloride hexahydrate and deionized water 0.005:0.02:1, adding potassium hydroxide according to the mass ratio of potassium hydroxide and cupric chloride 0.8:1, stirring for 4 h, transferring into a reaction kettle, suspending the foamed nickel / Co-B composite in the reaction solution according to the mass ratio of foamed nickel / Co-B composite and cupric chloride 5:1, reacting at 80℃ for 11 h, centrifuging, washing with deionized water in an amount of 200 times the mass of the foamed nickel / Co-B composite, and drying at 90℃ for 7 h.

[0041] The catalyst was applied to the hydrogenation deoxidization reaction of phenol, the solvent was n-tetradecane, the reaction temperature was 240℃, the reaction pressure was 2 MPa, and the reaction time was 4 h, and the conversion rate of phenol was 98%, and the main product was cyclohexane, and the selectivity of cyclohexane was 99%.

[0042] Example 4

[0043] The foamed nickel was cleaned with hydrochloric acid, acetone, ethanol and water in sequence, and dried at 80℃ for 12 h to obtain clean foamed nickel; a dilute sulfuric acid solution with a mass fraction of 1.8% was prepared, aniline was added according to the mass ratio of aniline and dilute sulfuric acid solution 0.08:1, and the electrolyte was obtained by stirring uniformly, the clean foamed nickel was cut according to the mass ratio of aniline and clean foamed nickel 0.7:1, the clean foamed nickel was clamped as a working electrode with a purple copper electrode clamp, Ag / AgCl was used as a reference electrode, and a platinum sheet was used as a counter electrode, the reaction was carried out at a constant potential of 1.1V for 10 min, and the polyaniline modified foamed nickel was obtained.

[0044] An aqueous solution of cobalt chloride hexahydrate with a mass fraction of 0.1% was prepared, sodium hydroxamate was added according to the mass ratio of sodium hydroxamate and aqueous solution of cobalt chloride hexahydrate 0.05:1, ammonium fluoride was added according to the mass ratio of ammonium fluoride and aqueous solution of cobalt chloride hexahydrate 0.03:1, stirring for 5 h, transferring into a reaction kettle, suspending the polyaniline modified foamed nickel in the reaction solution according to the mass ratio of polyaniline modified foamed nickel and aqueous solution of cobalt chloride hexahydrate 0.02:1, reacting at 100℃ for 12 h, centrifuging, washing with deionized water in an amount of 70 times the mass of the polyaniline modified foamed nickel, and drying at 80℃ for 10 h to obtain the polyaniline modified foamed nickel / Co(OH)F.

[0045] An aqueous solution of sodium hydroxide with a mass fraction of 3% was prepared, sodium borohydride was added according to the mass ratio of sodium borohydride and aqueous solution of sodium hydroxide 0.02:1 to obtain an aqueous solution of sodium borohydride, an aqueous solution of cobalt chloride with a mass fraction of 7% was prepared, the polyaniline modified foamed nickel / Co(OH)F was repeatedly immersed in the aqueous solution of cobalt chloride and the aqueous solution of sodium borohydride for 5 s in sequence, the number of repetitions was 35 times, drying at 85℃ for 6 h, transferring into a tube furnace, passing nitrogen, heating to 350℃, and calcining for 3 h to obtain the foamed nickel / Co-B composite.

[0046] An aqueous solution containing copper chloride and cobalt nitrate hexahydrate was prepared according to a mass ratio of copper chloride, cobalt nitrate hexahydrate and deionized water of 0.001:0.01:1, urea was added according to a mass ratio of urea to copper chloride of 1.6:1, stirred for 1 h, transferred to a reaction kettle, the foamed nickel / Co-B composite was suspended in the reaction solution according to a mass ratio of the foamed nickel / Co-B composite to copper chloride of 15:1, reacted at 90°C for 12 h, centrifuged, washed with deionized water in an amount of 100 times the mass of the foamed nickel / Co-B composite, and dried at 60°C for 11 h to obtain a phenolic compound hydrodeoxygenation catalyst.

[0047] The catalyst was applied to a 2-methoxyphenol hydrodeoxygenation reaction, the solvent was n-dodecane, the reaction temperature was 270°C, the reaction pressure was 4 MPa, the reaction time was 10 h, the conversion rate of 2-methoxyphenol was 98%, and the main product was cyclohexane with a selectivity of 72%.

[0048] Example 5

[0049] The foamed nickel was sequentially cleaned with hydrochloric acid, acetone, ethanol and water, and dried at 90°C for 9 h to obtain clean foamed nickel; a dilute sulfuric acid solution with a mass fraction of 0.2% was prepared, aniline was added according to a mass ratio of aniline to the dilute sulfuric acid solution of 0.09:1, and stirred uniformly to obtain an electrolyte, the clean foamed nickel was cut according to a mass ratio of aniline to clean foamed nickel of 2:1, and the clean foamed nickel was clamped as a working electrode with a red copper electrode clamp, Ag / AgCl was used as a reference electrode, and a platinum sheet was used as a counter electrode, and a polyaniline modified foamed nickel was obtained by reacting at a constant potential of 1.2V for 15 min.

[0050] A cobalt nitrate hexahydrate aqueous solution with a mass fraction of 0.7% was prepared, sodium hydroxide was added according to a mass ratio of sodium hydroxide to the cobalt nitrate hexahydrate aqueous solution of 0.03:1, lithium fluoride was added according to a mass ratio of lithium fluoride to the cobalt nitrate hexahydrate aqueous solution of 0.01:1, stirred for 2 h, transferred to a reaction kettle, the polyaniline modified foamed nickel was suspended in the reaction solution according to a mass ratio of the polyaniline modified foamed nickel to the cobalt nitrate hexahydrate aqueous solution of 0.01:1, reacted at 130°C for 9 h, centrifuged, washed with deionized water in an amount of 170 times the mass of the polyaniline modified foamed nickel, and dried at 70°C for 8 h to obtain a polyaniline modified foamed nickel / Co(OH)F.

[0051] The 2% by mass sodium hydroxide aqueous solution was prepared, 0.01:1 by mass ratio of sodium borohydride to the sodium hydroxide aqueous solution was added to obtain the sodium borohydride aqueous solution, the 2% by mass cobalt chloride aqueous solution was prepared, the polyaniline modified foam nickel / Co(OH)F was immersed in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution for 15 s, respectively, the number of repetitions was 45 times, the foam nickel / Co-B composite was obtained by drying at 70℃ for 9 h, transferring into a tube furnace, passing argon, heating to 400℃, and calcining for 2.5 h.

[0052] The aqueous solution containing copper sulfate and cobalt chloride hexahydrate was prepared according to the mass ratio of copper sulfate, cobalt chloride hexahydrate and deionized water 0.009:0.017:1, 2:1 by mass ratio of sodium hydroxide to copper chloride was added, stirred for 3.5 h, transferred into a reaction kettle, 10:1 by mass ratio of foam nickel / Co-B composite to copper chloride, the foam nickel / Co-B composite was suspended in the reaction solution, reacted at 100℃ for 11 h, centrifuged, washed with 140 times the mass of deionized water of the foam nickel / Co-B composite, and dried at 65℃ for 12 h to obtain the phenolic compound hydrodeoxygenation catalyst.

[0053] The catalyst was applied to the hydrodeoxygenation reaction of 2-methoxyphenol, the solvent was n-dodecane, the reaction temperature was 265℃, the reaction pressure was 3 MPa, and the reaction time was 8 h, the conversion rate of 2-methoxyphenol was 92%, and the main product was cyclohexane, and the selectivity of cyclohexane was 78%.

[0054] Example 6

[0055] The foam nickel was sequentially cleaned with hydrochloric acid, acetone, ethanol and water, and dried at 95℃ for 7 h to obtain clean foam nickel; the 0.6% by mass dilute sulfuric acid solution was prepared, 0.1:1 by mass ratio of aniline to the dilute sulfuric acid solution was added to obtain an electrolyte, 1.4:1 by mass ratio of aniline to clean foam nickel was cut to obtain the clean foam nickel, the clean foam nickel was clamped as a working electrode with a red copper electrode clamp, Ag / AgCl was used as a reference electrode, and a platinum sheet was used as a counter electrode, the reaction was carried out at a constant potential of 1.1 V for 5 min to obtain the polyaniline modified foam nickel.

[0056] Prepare a 1.4% (w / w) aqueous solution of cobalt nitrate hexahydrate. Add thiourea at a mass ratio of 0.07:1 and sodium fluoride at a mass ratio of 0.02:1. Stir for 5 hours, then transfer to a reaction vessel. Suspend polyaniline-modified nickel foam in the reaction solution at a mass ratio of 0.05:1 and react at 140°C for 8 hours. Centrifuge, wash with 200 times the mass of the polyaniline-modified nickel foam in deionized water, and dry at 90°C for 7 hours to obtain polyaniline-modified nickel foam / Co(OH)F.

[0057] Prepare a 4% sodium hydroxide aqueous solution. Add sodium borohydride to the sodium hydroxide aqueous solution at a mass ratio of 0.08:1 to obtain a sodium borohydride aqueous solution. Prepare a 10% cobalt chloride aqueous solution. Immerse polyaniline modified nickel foam / Co(OH)F in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution sequentially for 10 seconds each time, repeating the process 50 times. Dry at 75°C for 8 hours. Transfer the mixture to a tube furnace, introduce nitrogen gas, raise the temperature to 500°C, and calcine for 2 hours to obtain the nickel foam / Co-B composite.

[0058] An aqueous solution containing copper sulfate and cobalt chloride hexahydrate was prepared at a mass ratio of 0.017:0.001:1 (copper sulfate, cobalt chloride hexahydrate, and deionized water). Potassium hydroxide was added at a mass ratio of 1.8:1 (potassium hydroxide to copper chloride). The mixture was stirred for 2.5 h and then transferred to a reaction vessel. The nickel foam / Co-B composite was suspended in the reaction solution at a mass ratio of 20:1 (nickel foam / Co-B composite to copper sulfate). The mixture was reacted at 140 °C for 8 h, centrifuged, washed with 50 times the mass of the nickel foam / Co-B composite in deionized water, and dried at 85 °C for 6 h to obtain a phenolic compound hydrodeoxygenation catalyst.

[0059] The catalyst was applied to the hydrodeoxygenation reaction of anisole at a reaction temperature of 265 °C, a reaction pressure of atmospheric pressure, and a weight hourly space velocity of 2.4 h⁻¹. -1 The conversion rate of anisole was 95%, the main product was cyclohexane, and the selectivity of cyclohexane was 94%.

[0060] Example 7

[0061] The nickel foam is cleaned with hydrochloric acid, acetone, ethanol and water in sequence, dried at 85℃ for 10h to obtain clean nickel foam; a dilute sulfuric acid solution with a mass fraction of 2% is prepared, aniline is added according to a mass ratio of aniline to the dilute sulfuric acid solution of 0.05:1, and stirred uniformly to obtain an electrolyte, the clean nickel foam is cut according to a mass ratio of aniline to clean nickel foam of 1.8:1, the clean nickel foam is clamped as a working electrode with a red copper electrode holder, Ag / AgCl is used as a reference electrode, and a platinum plate is used as a counter electrode, and polyaniline modified nickel foam is obtained by reacting at a constant potential of 1.1V for 5min.

[0062] A cobalt chloride hexahydrate aqueous solution with a mass fraction of 0.1% is prepared, urea is added according to a mass ratio of urea to the cobalt chloride hexahydrate aqueous solution of 0.08:1, sodium fluoride is added according to a mass ratio of sodium fluoride to the cobalt chloride hexahydrate aqueous solution of 0.05:1, stirred for 4h, transferred into a reaction kettle, and the polyaniline modified nickel foam is suspended in the reaction solution according to a mass ratio of the polyaniline modified nickel foam to the cobalt chloride hexahydrate aqueous solution of 0.03:1, reacted at 150℃ for 9h, centrifuged, washed with deionized water with a volume of 180 times the mass of the polyaniline modified nickel foam, and dried at 80℃ for 6h to obtain polyaniline modified nickel foam / Co(OH)F.

[0063] A sodium hydroxide aqueous solution with a mass fraction of 5% is prepared, sodium borohydride is added according to a mass ratio of sodium borohydride to the sodium hydroxide aqueous solution of 0.1:1 to obtain a sodium borohydride aqueous solution, a cobalt chloride aqueous solution with a mass fraction of 9% is prepared, and the polyaniline modified nickel foam / Co(OH)F is repeatedly immersed in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution for 20s in sequence, the number of repetitions is 25, dried at 85℃ for 10h, transferred into a tube furnace, nitrogen is introduced, heated to 450℃, and calcined for 2h to obtain a nickel foam / Co-B composite.

[0064] A water solution containing copper nitrate and cobalt nitrate hexahydrate is prepared according to a mass ratio of copper nitrate, cobalt nitrate hexahydrate and deionized water of 0.02:0.01:1, potassium hydroxide is added according to a mass ratio of potassium hydroxide to copper nitrate of 1.8:1, stirred for 4.5h, transferred into a reaction kettle, and the nickel foam / Co-B composite is suspended in the reaction solution according to a mass ratio of the nickel foam / Co-B composite to copper nitrate of 18:1, reacted at 150℃ for 9h, centrifuged, washed with deionized water with a volume of 80 times the mass of the nickel foam / Co-B composite, and dried at 65℃ for 12h to obtain a phenolic compound hydrogenation and deoxidation catalyst.

[0065] The catalyst is applied to a hydrogenation and deoxidation reaction of anisole, the reaction temperature is 265℃, the reaction pressure is normal pressure, the weight hourly space velocity of the reaction is 1.9h -1 , the conversion rate of anisole is 96%, and the main product is methylcyclohexane, and the selectivity of methylcyclohexane is 95%.

[0066] Comparative Example 1

[0067] Prepared according to the method of Example 1, except that step (4) was not performed and only steps (1)-(3) were completed, resulting in a foamed nickel / Co-B composite.

[0068] Copper cobalt hydroxide was also prepared according to the method of step (4) of Example 1.

[0069] The foamed nickel / Co-B composite was physically mixed with the copper cobalt hydroxide (mass ratio 1:1) and then applied to the hydrodeoxygenation of phenol. The solvent was n-dodecane, the reaction temperature was 230°C, the reaction pressure was 2 MPa, and the reaction time was 4 h. The conversion of phenol was 40.3% and the selectivity of cyclohexane was 75.4%.

[0070] Thus, it can be seen that the deposition of copper cobalt hydroxide on the surface of the foamed nickel / Co-B composite can greatly improve the catalytic activity and selectivity of the catalyst in the hydrodeoxygenation of phenolic compounds.

[0071] The above description is only the preferred embodiments of the present application, and does not limit the present application in any form. Any modification, equivalent replacement and improvement of the above embodiments made by those skilled in the art according to the technical essence of the present application, without departing from the technical solution of the present application, shall still fall within the protection scope of the present application.

Claims

1. A catalyst for the hydrodeoxygenation of phenolic compounds, characterized in that, The catalyst is a supported catalyst, comprising an active support and a carrier; wherein the carrier is nickel foam, and the active support is a composite of flocculent CoB nanomaterials and sheet-like copper cobalt hydroxide; firstly, polyaniline is deposited on nickel foam using electrochemical deposition, then Co(OH)F is deposited on nickel foam using the surface modification effect of polyaniline, and a nickel foam / Co-B composite is prepared using reduction borylation, and finally copper cobalt hydroxide is deposited on the surface of the nickel foam / Co-B composite to obtain a phenolic compound hydrodeoxygenation catalyst.

2. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 1, characterized in that, First, polyaniline was deposited onto nickel foam using electrochemical deposition. Then, Co(OH)F was deposited on the nickel foam by surface modification of polyaniline, and a nickel foam / Co-B composite was prepared by reduction borylation. Finally, copper cobalt hydroxide was deposited on the surface of the nickel foam / Co-B composite to obtain a phenolic compound hydrodeoxygenation catalyst.

3. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 2, characterized in that, Includes the following steps: (1) Clean and dry the foamed nickel to obtain clean foamed nickel; prepare a dilute sulfuric acid solution with a mass fraction of 0.2% to 2%, add aniline according to the mass ratio of aniline to dilute sulfuric acid solution of 0.05:1 to 0.1:1, stir evenly to obtain electrolyte, cut the clean foamed nickel according to the mass ratio of aniline to clean foamed nickel of 0.5:1 to 2:1, clamp the clean foamed nickel with copper electrode clamp as working electrode, use Ag / AgCl as reference electrode, and use platinum sheet as counter electrode, react at a constant potential of 0.8 to 1.2V for 5 to 40 min to obtain polyaniline modified foamed nickel; (2) Prepare a cobalt salt aqueous solution with a mass fraction of 0.1% to 2%. Add urea or thiourea at a mass ratio of 0.02:1 to 0.1:1 with the cobalt salt aqueous solution. Add fluoride at a mass ratio of 0.01:1 to 0.05:1 with the cobalt salt aqueous solution. Stir for 2 to 6 hours. Transfer to a pressurized sealed container. Suspend the polyaniline modified foam nickel obtained in step (1) in the reaction solution at a mass ratio of 0.01:1 to 0.05:1 with the cobalt salt aqueous solution. React at 100 to 150°C for 8 to 12 hours. Centrifuge and wash with 50 to 200 times the mass of the polyaniline modified foam nickel with water. Dry at 60 to 90°C for 6 to 12 hours to obtain polyaniline modified foam nickel / Co(OH)F. (3) Prepare a sodium hydroxide aqueous solution with a mass fraction of 0.2% to 5%, add sodium borohydride at a mass ratio of 0.01 to 0.1:1 to obtain a sodium borohydride aqueous solution, prepare a cobalt chloride aqueous solution with a mass fraction of 2% to 10%, and repeatedly immerse the polyaniline modified foam nickel / Co(OH)F obtained in step (2) in the cobalt chloride aqueous solution and the sodium borohydride aqueous solution for 5 to 20 seconds, repeating 20 to 50 times, drying at 60 to 90°C for 6 to 12 hours, transferring to a heating device, introducing nitrogen or argon, heating to 300 to 500°C, and calcining for 2 to 5 hours to obtain the foam nickel / Co-B composite. (4) Prepare an aqueous solution containing copper salt and cobalt salt at a mass ratio of copper salt, cobalt salt and water of 0.001-0.02:0.001-0.02:

1. Add alkaline substance at a mass ratio of alkaline substance to copper salt of 0.2:1-2:

1. Stir for 1-4 hours and transfer to a pressurized sealed container. Suspend the nickel foam / Co-B complex in the reaction solution at a mass ratio of nickel foam / Co-B complex to copper salt of 5:1-20:

1. React at 80-150℃ for 8-12 hours. Centrifuge and wash with 50-200 times the mass of nickel foam / Co-B complex in water. Dry at 60-90℃ for 6-12 hours to obtain a phenolic compound hydrogenation deoxygenation catalyst.

4. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 3, characterized in that, The process of cleaning and drying the nickel foam in step (1) to obtain clean nickel foam is as follows: the nickel foam is cleaned in sequence with hydrochloric acid, acetone, ethanol and water, and dried at 80-100℃ for 6-12 hours to obtain clean nickel foam.

5. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 3, characterized in that, The cobalt salt mentioned in step (2) is one of cobalt nitrate hexahydrate and cobalt chloride hexahydrate, and the fluoride is one of ammonium fluoride, sodium fluoride and lithium fluoride.

6. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 3, characterized in that, The pressure-bearing closed container mentioned in steps (2) and (4) is a reaction vessel.

7. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 3, characterized in that, The heating device mentioned in step (3) is a tubular furnace.

8. The method for preparing the phenolic compound hydrodeoxygenation catalyst according to claim 3, characterized in that, The copper salt mentioned in step (4) is one of copper sulfate, copper nitrate, and copper chloride; the cobalt salt is cobalt nitrate hexahydrate or cobalt chloride hexahydrate; and the alkaline substance is one of sodium hydroxide, potassium hydroxide, and urea.

9. The application of the phenolic compound hydrodeoxygenation catalyst according to claim 1 in the hydrodeoxygenation reaction of phenolic compounds.

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