Method and catalyst for producing methylbenzyl alcohol from ethanol by catalytic conversion

Abstract

The present invention relates to methods and catalysts for producing methylbenzyl alcohol from ethanol by catalytic conversion, and belongs to the field of chemical engineering and technology. The present invention develops a route of producing methylbenzyl alcohol starting from green and sustainable ethanol and provide corresponding catalysts used for the catalytic conversion route. This innovative reaction route has several advantages, such as, simple process, eco-friendly property, and easy separation of products, as compared with a traditional petroleum-based route. This present route has a reaction temperature of 150-450° C. and total selectivity of 72% for methylbenzyl alcohol, and has good industrial application prospect. The innovation of this patent comprises the catalysts synthesis and the reaction route.

Claims

1. A method for producing methylbenzyl alcohol from ethanol by catalytic conversion, comprising the following steps: (1) production of dehydrogenation catalyst, comprising (1.1) preparing an aqueous solution of transition metal salts and/or and an alcohol solution of the transition metal salts; wherein a concentration of the aqueous solution of the transition metal salts is 0.075 g/mL-0.75 g/mL; a concentration of the alcohol solution of the transition metal salts is 0.075-0.225 g/mL; the transition metal salts are selected from one or a combination of more than one of chloride, nitrate, diacetone, sulfate and acetate; alcohol solvent is methanol and/or ethanol, (1.2) using an incipient wetness impregnation method to impregnate a support for 1-3 times using the aqueous solution or the alcohol solution of the transition metal salts prepared in the step (1.1); after impregnation, staying obtained mixture at room temperature for 0.1-2 h; (1.3) placing the obtained mixture from the step (1.2) into a 50° C. oven for drying for 0.1-20 h; (1.4) drying the dried product in the step (1.3) at 100-150° C. for 0.5-2 h, and treating a dehydrogenation catalyst precursor in an inert atmosphere and a hydrogen atmosphere in sequence or in the hydrogen atmosphere directly to obtain supported transition metal catalyst, which is the dehydrogenation catalyst, recorded as transition metal/support; wherein the transition metal is selected from one or a combination of more than one of Co, Ni, Cu, Ag, Pd, Rh, Ru, Pt, Ir, Zn and Y; the support is selected from carbon, Al.sub.2O.sub.3, SiO.sub.2, ZrO.sub.2, ZnO and MgO; if the support is carbon, the dehydrogenation catalyst precursor is treated in the inert atmosphere at 350-450° C. for 1-5 h, and then reduced in the hydrogen atmosphere at 350-600° C. for 0.5-5 h; if the support is Al.sub.2O.sub.3, SiO.sub.2, ZrO.sub.2, ZnO or MgO, the dehydrogenation catalyst precursor is reduced directly in the hydrogen atmosphere at 350-600° C. for 2-5 h; (2) production of aromatization catalyst, comprising: (2.1) dissolving nitrates of metals A, B, C, D and E in water to prepare corresponding aqueous solutions; (2.2) dissolving diammonium phosphate in water to prepare the corresponding aqueous solution; (2.3) adding the nitrate solutions prepared in the step (2.1) in the aqueous solution prepared in the step (2.2) dropwise, and fully stirring; wherein a molar ratio of metals to phosphorus is 1.5-1.67; (2.4) using ammonia water to adjust the pH value of the turbid solution obtained in the step (2.3) to 8-12, and then stirring at 50-80° C. for 24 h; (2.5) drying the precipitates obtained in the step (2.4) in a treatment atmosphere at 25-200° C. for 1-10 h, and then conducting heat treatment at 350-700° C. for 0.5-10 h to obtain metal hydroxy phosphate, which is the aromatization catalyst; the aromatization catalyst is metal hydroxy phosphate (A.sub.xB.sub.yC.sub.zD.sub.mE.sub.n(OH).sub.2(PO.sub.4).sub.6, x+y+z+m+n=9-10, 9-10≥x,y,z,m,n≥0) and metallic phosphate (A.sub.xB.sub.yC.sub.zD.sub.mE.sub.n(PO.sub.4).sub.2, x+y+z+m+n=3, 3≥x,y,z,m,n≥0); wherein the metals A, B, C, D and E are the same or different and are selected from one or a combination of more than one of Mg, Ca, Sr, Ba, Pb, Cu, Ni, Co, Zn, Zr and Hf; when the aromatization catalyst contains the transition metal Cu, Ni, Co, Zn, Zr and Hf, the precipitates obtained in the step (2.4) are heat treated at 350-550° C.; (3) pelleting and packing the dehydrogenation catalyst and the aromatization catalyst, comprising: (3.1) respectively tabletting, shaping and screening the dehydrogenation catalyst and the aromatization catalyst prepared in the above steps to a specified particle size; (3.2) packing the dehydrogenation catalyst and the aromatization catalyst shaped in the step (3.1) in sequence in a single fixed tube, and separating the dehydrogenation catalyst and the aromatization catalyst by quartz wool; (3.3) reducing a double bed catalyst obtained in the step (3.2) in hydrogen atmosphere at 350-750° C. for 1-5 h; and (4) at reaction temperature of 150-450° C. and reaction pressure of 1-50 atm, introducing ethanol into a reactor packed with the double bed catalyst to produce methylbenzyl alcohol.

2. The method according to claim 1, wherein in the step (1.4), the inert atmosphere is one or a combination of more than one of He, Ar and N.sub.2.

3. The method according to claim 2, wherein in the step (2.5), the treatment atmosphere is one or a combination of more than one of Hz, He, Ar, N.sub.2 and O.sub.2.

4. The method according to claim 1, wherein in the step (1.4) and the step (3.3), the hydrogen reduction concentration is one of 5-20 vol % H.sub.2/N.sub.2, H.sub.2/He and H.sub.2/Ar.

5. The method according to claim 2, wherein in the step (1.4) and the step (3.3), the hydrogen reduction concentration is one of 5-20 vol % H.sub.2/N.sub.2, H.sub.2/He and H.sub.2/Ar.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an XRD spectrum of 10Cu/carbon catalyst in embodiment 1;

(2) FIG. 2 is an XRD spectrum of 10Cu/SiO.sub.2 catalyst in embodiment 2;

(3) FIG. 3 shows different catalyst mixing manners in embodiment 6;

(4) FIG. 4 is data of specific product distributions at reaction temperature of 225° C. in embodiment 8.

DETAILED DESCRIPTION

(5) The present invention is described below in detail through some embodiments. However, the present invention is not limited to these embodiments.

(6) The dehydrogenation catalyst is represented by wMetal/support, wherein w=weight percent of metal loading in total weight of the catalysts x100.

(7) The aromatization catalyst is represented by HAP-M and PO-M, wherein HAP represents hydroxymetallic apatite; PO represents metal phosphate; and M refers to metal and is one or more of Mg, Ca, Sr, Ba, Pb, Cu, Ni, Co, Zn, Zr, Hf, etc.

Embodiment 1

(8) Synthesis of Carbon Supported Cu Catalyst:

(9) (1) carbon support is dried at 120° C. for 2 h to remove physical adsorption water on its surface;

(10) (2) Cu(NO.sub.3).sub.2.3H.sub.2O aqueous solution with a mass concentration of 0.75 g/mL is prepared;

(11) (3) at 25° C., an incipient wetness impregnation method is used to treat the solution in the step (2) on carbon to stand for 0.1 h;

(12) (4) the obtained mixture after staying for 0.1 h at room temperature is then dried at 50° C. for 0.5 h to obtain corresponding catalyst precursors;

(13) (5) the precursor obtained in the step (4) is dried at 140° C. for 0.5 h, treated in inert atmosphere at 350° C. for 1 h, and then treated in hydrogen atmosphere at 450° C. for 2 h to obtain carbon supported Cu catalyst, which is denoted as 10Cu/carbon (entry 1 in Table 1).

(14) The XRD spectrum of 10Cu/carbon catalyst is shown in FIG. 1.

(15) TABLE-US-00001 TABLE 1 Corresponding Relationship between Sample Number and Preparation Conditions in Embodiment 1 Reduc- Metal tion Load- Concen- Temper- Cata- ing/ Sup- tration/ ature/ Entry lyst wt % port Metals Solvent g/mL ° C. 1 10u/ 10 Carbon Copper Water 0.75 450 Carbon nitrate 2 10Cu/ 10 SiO.sub.2 Copper Water 0.75 450 SiO.sub.2 nitrate 3 10Cu/ 10 Al.sub.2O.sub.3 Copper Water 0.75 450 Al.sub.2O.sub.3 nitrate 4 10Cu/ 10 ZrO.sub.2 Copper Water 0.75 450 ZrO.sub.2 nitrate 5 10Cu/ 10 ZnO Copper Water 0.75 450 ZnO nitrate 6 10Cu/ 10 MgO Copper Water 0.75 450 MgO nitrate 7 10Cu/C/ 10 C/SiO.sub.2 Copper Water 0.75 450 SiO.sub.2 nitrate 8 5Cu/ 5 Carbon Copper Water 0.4  450 carbon nitrate 9 10Ni/ 10 Carbon Nickel Water 0.8  600 carbon nitrate

Embodiment 2

(16) Synthesis of SiO.sub.2 Supported Cu Catalyst:

(17) (1) SiO.sub.2 support is dried at 120° C. for 2 h to remove physical adsorption water on its surface;

(18) (2) Cu(NO.sub.3).sub.2.3H.sub.2O aqueous solution with a mass concentration of 0.75 g/mL is prepared;

(19) (3) at 25° C., an incipient wetness impregnation method is used to treat the solution in the step (2) on SiO.sub.2 to stand for 2 h;

(20) (4) the obtained mixture after staying for 2 h at room temperature is then dried at 50° C. for 8 h to obtain corresponding catalyst precursors;

(21) (5) the precursor obtained in the step (4) is treated in hydrogen atmosphere at 450° C. for 2 h to obtain SiO.sub.2 supported Cu catalyst, which is denoted as 10Cu/SiO.sub.2 (entry 2 in Table 1).

(22) The XRD spectrum of 10Cu/SiO.sub.2 catalyst is shown in FIG. 2.

(23) The preparation conditions of other oxide supported metal catalysts are the same as those in embodiment 2. The corresponding relationship between the sample number and the preparation conditions are shown in Table 1.

Embodiment 3

(24) Synthesis of Metal Hydroxy Phosphate Ca.sub.8Co.sub.2(OH).sub.2(PO.sub.4).sub.6:

(25) (1) calcium nitrate and cobalt nitrate are dissolved in water to prepare aqueous solution with a total mole fraction of 0.6 M;

(26) (2) diammonium phosphate is dissolved in water to prepare aqueous solution with a mole fraction of 0.4 M, wherein the molar ratio of Ca+Co to P is 1.67;

(27) (3) the calcium nitrate and cobalt nitrate solution prepared in the step (1) is added in the aqueous solution prepared in the step (2) dropwise (10 mL/min), and fully stirred for 60 min;

(28) (4) stronger ammonia water (−25 wt %) is added to the turbid solution obtained in the step (3) to adjust the pH value of the whole system to above 11, and then stirred at 80° C. for 24 h;

(29) (5) pink precipitates obtained in the step (4) are dried in specific atmosphere at 50° C. for 10 h, and then roasted at 550° C. for 2 h to obtain Ca.sub.8Co.sub.2(OH).sub.2(PO.sub.4).sub.6.

(30) The atomic ratios of Ca and Co can be adjusted by controlling the mass ratio of added calcium nitrate to added cobalt nitrate, and the preparation method is the same as that in embodiment 3. The corresponding relationship between the sample number and the preparation conditions are shown in Table 2.

(31) The species and ratio of metal atoms can be adjusted by controlling the added nitrate, and the preparation method is the same as that in embodiment 3. The corresponding relationship between the sample number and the preparation conditions are shown in Table 2.

(32) TABLE-US-00002 TABLE 2 Corresponding Relationships between Sample Number and Preparation Conditions in Embodiment 3 Reduction/Treatment Entry Catalyst Metals Temperature/° C. 1 HAP-8Ca2Co Calcium nitrate 550 and cobalt nitrate 2 HAP-5Ca5Co Calcium nitrate 550 and cobalt nitrate 3 HAP-Ca Calcium nitrate 600 4 HAP-Sr Strontium nitrate 600 5 HAP-Mg Magnesium nitrate 600 6 HAP-Ba Barium nitrate 600 7 PO-2Ca1Co Calcium nitrate 550 and cobalt nitrate 8 PO-Ca Calcium nitrate 600 9 PO-Mg Magnesium nitrate 600

Embodiment 4

(33) Synthesis of Metal Calcium Phosphate Ca.sub.2Co(PO.sub.4).sub.2:

(34) (1) calcium hydroxide and cobalt hydroxide (Ca.sup.2+/Co.sup.2+=2:1, molar ratio) are dispersed in water to prepare corresponding solid suspension liquid, and stirred;

(35) (2) 10 wt % of H.sub.3PO.sub.4 solution is prepared;

(36) (3) The phosphoric acid solution prepared in the step (2) is added in the solid suspension liquid prepared in the step (1) and fully stirred, the amount of the phosphoric acid added is controlled by the pH value of the suspended solids, and then intense stirring is conducted for 3 h;

(37) (4) While precipitates obtained in the step (3) are dried in specific atmosphere at 25-200° C. for 2 h, and then roasted at 600° C. for 2 h to obtain Ca.sub.2Co(PO.sub.4).sub.2.

(38) The atomic ratios of Ca and Co can be adjusted by controlling the mass ratio of added calcium nitrate to added cobalt nitrate, and the preparation method is the same as that in embodiment 4. The corresponding relationship between the sample number and the preparation conditions are shown in Table 2.

(39) The species and ratio of metal atoms can be adjusted by controlling the added nitrate, and the preparation method is the same as that in embodiment 4. The corresponding relationship between the sample number and the preparation conditions are shown in Table 2.

Embodiment 5

(40) Catalytic Activity of Dehydrogenation and Aromatization Composite Catalysts of the Single-Reactor and Double-Bed Structure from Ethanol to Methylbenzyl Alcohol

(41) Ethanol upgrading is studied in a fix-bed, atmosphere pressure reactor by feeding ethanol as reactant. Reaction conditions are as follows: the catalyst is first packed in the fix-bed reactor with an inner diameter of 8 mm and kept at 225° C. Then, ethanol liquid is fed in a rate of 0.3 mL/h After steady, ethanol conversion and products distribution are analyzed by an on-line gas chromatography (GC). The corresponding relationship between sample number and ethanol upgrading activity is shown in Table 3.

(42) TABLE-US-00003 TABLE 3 Corresponding Relationships between Sample Number and Ethanol Conversion and Methylbenzyl Alcohol Selectivity in Embodiment 5 Entry Catalyst Conversion/% Selectivity/% 1 10Cu/carbon//HAP-8Ca.sub.2Co 16.1 72.5 2 10Cu/SiO.sub.2//HAP-8Ca2Co 15.5 73.1 3 10Cu/Al.sub.2O.sub.3//HAP-8Ca2Co 19.0 40.5 4 10Cu/ZrO.sub.2//HAP-8Ca2Co 20.1 45.0 5 10Cu/ZnO//HAP-8Ca2Co 16.5 72.1 6 10Cu/MgO//HAP-8Ca2Co 16.2 71.2 7 10Cu/C/SiO.sub.2//HAP-8Ca2Co 17.6 70.1 8 5Cu/carbon//HAP-8Ca.sub.2Co 15.9 71.1 9 10Ni/carbon//HAP-8Ca.sub.2Co 15 65.6 10 10Cu/carbon//HAP-5Ca.sub.5Co 17.6 72.8 11 10Cu/carbon//HAP-Ca 15.5 60.1 12 10Cu/carbon//HAP-Sr 14.9 61.0 13 10Cu/carbon//HAP-Mg 17.1 59.5 14 10Cu/carbon//HAP-Ba 13.5 54.9 15 10Cu/carbon//PO-2Ca.sub.1Co 15.9 32.5 16 10Cu/carbon//PO-Ca 16.0 36.2 17 10Cu/ carbon//PO-Mg 16.2 30.1

Embodiment 6

(43) Effect of Mixing Manners of Dehydrogenation and Aromatization Composite Catalysts on Selectivity of Methylbenzyl Alcohol

(44) Ethanol upgrading is studied in a fix-bed, atmosphere pressure reactor by feeding ethanol as reactant, the dehydrogenation catalyst is 10Cu/carbon, and the aromatization catalyst is HAP-8Ca.sub.2Co. Reaction conditions are as follows: at atmosphere pressure and reaction temperature of 225° C., ethanol liquid is fed in a rate of 0.3 mL/h, and WHSV=1.0 h.sup.−1. Three catalyst mixing manners are used: single reactor and single bed (1), single reactor and double beds (2) and double beds (3). After steady, ethanol conversion and products distribution are analyzed by an on-line gas chromatography (GC). Reaction results are shown in Table 4.

(45) The catalyst mixing manners are shown in FIG. 3.

(46) TABLE-US-00004 TABLE 4 Study of Effect of Dehydrogenation and Aromatization Composite Catalyst Mixing Manner on Methylbenzyl Alcohol Selectivity in Embodiment 6 Mixing Manner Conversion/% Selectivity/% (1) 14.5 25.1 (2) 16.1 72.5 (3) 17.5 71.8

Embodiment 7

(47) Product Distribution of Ethanol with Different Concentrations by Catalytic Conversion of Dehydrogenation and Aromatization Composite Catalysts of Single-Reactor and Double-Bed Structure

(48) Ethanol upgrading is studied in a fix-bed, atmosphere pressure reactor by feeding ethanol as reactant, the dehydrogenation catalyst is 10Cu/carbon, and the aromatization catalyst is HAP-8Ca.sub.2Co. Reaction conditions are as follows: the catalyst is first packed in the fix-bed reactor with an inner diameter of 8 mm and kept at 225° C. Then, ethanol liquid is fed in a rate of 0.3 mL/h, and WHSV=1.0 h.sup.−1. After steady, ethanol conversion and products distribution are analyzed by an on-line gas chromatography (GC). Reaction results are shown in Table 5.

(49) TABLE-US-00005 TABLE 5 Study of Effect of Ethanol Concentration on Methylbenzyl Alcohol Selectivity in Embodiment 7 Feeding (mL/h) Conversion/% Selectivity/% 0.05 34.8 50.1 0.1 27.5 58.9 0.15 21.0 62.3 0.2 18.6 67.1 0.27 16.1 72.5 0.32 13.4 72.1 2.7 2.2 28.9

Embodiment 8

(50) Product Distribution of Ethanol by Catalytic Conversion of Dehydrogenation and Aromatization Composite Catalysts of Single-Reactor and Double-Bed Structure at Different Temperatures

(51) Ethanol upgrading is studied in a fix-bed, atmosphere pressure reactor by feeding ethanol as reactant, the dehydrogenation catalyst is 10Cu/carbon, and the aromatization catalyst is HAP-8Ca.sub.2Co. Reaction conditions are as follows: the catalyst is first packed in the fix-bed reactor with an inner diameter of 8 mm and kept at different reaction temperature (100-450° C.). Then, ethanol liquid is fed in a rate of 0.3 mL/h, and WHSV=1.0 h.sup.−1. After steady, ethanol conversion and products distribution are analyzed by an on-line gas chromatography (GC). Reaction results are shown in Table 6.

(52) The product distribution at reaction temperature of 225° C. is shown in FIG. 4.

(53) TABLE-US-00006 TABLE 6 Product Distribution of Ethanol by catalytic conversion at Different Temperatures in Embodiment 8 Temperature Conversion/% Selectivity/% 150 1.2 42.7 175 3.9 61.1 200 8.9 68.3 225 16.1 72.5 250 20.4 67.2 275 28.7 65.0 300 37.7 65.3 325 36.7 54.0 350 45.8 43.1 400 75.1 22.0