Method and catalyst for producing benzyl alcohol and homologues thereof from short-chain alcohols by catalytic conversion

Abstract

Methods and catalysts for producing benzyl alcohol and homologues thereof from short-chain alcohols by catalytic conversion are disclosed. The methods and catalysts develop a new route for benzyl alcohols and ethyl benzyl alcohols production through cross coupling-aromatization reaction using short-chain alcohols as reactants and provide corresponding catalysts required for the above catalytic reaction. It is emphasized on a single bed catalyst to produce benzyl alcohol and its homologues in one step, and is expected to become an important alternative route for the production of benzyl alcohol and its homologues. A route and corresponding catalysts for directly producing benzyl alcohol and ethyl benzyl alcohol through coupling-aromatization reaction starting from low carbon alcohols are provided. The selectivity of the benzyl alcohol is up to 35%, and the total selectivity of the ethyl benzyl alcohol is up to 11%.

Claims

1. A method for producing benzyl alcohol or ethyl benzyl alcohol thereof from short-chain alcohols by catalytic conversion, comprising the following steps: (1) preparing transition metals aqueous solution and/or transition metals alcohol solution; (2) using an incipient wetness impregnation method to impregnate hydroxyl phosphates using the transition metals aqueous solution and/or transition metals alcohol solution prepared in the step (1); after impregnation, stayed at room temperature for 0.5-2 h; (3) placing the obtained mixture from the step (2) into a 100° C. oven for drying for 8-20 h; (4) conducting oxidation on the dried product in the step (3) at 250-550° C. for 1 to 5 h in an air atmosphere, and then treating under hydrogen atmosphere at 325-700° C. for 0.5-2 h to obtain transition metal-hydroxyl phosphate catalysts; wherein the transition metal-hydroxyl phosphate catalysts comprise two parts: transition metals and hydroxyl phosphate; loading of the transition metals is 0.01-50 wt % of the weight of the hydroxyl phosphate; the transition metals are one or a combination of more than one of Co, Ni, Cu, Ag, Ir, Zn and Y; the hydroxyl phosphate is A.sub.xB.sub.yC.sub.zD.sub.mE.sub.n(OH).sub.2(PO.sub.4).sub.6; in the formula, x+y+z+m+n=9-10, 9-10≥ x,y,z,m,n≥ 0, wherein 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 and Pb; (5) at reaction temperature of 150-450 ° C. and reaction pressure of 1-50 atm, introducing mixture of ethanol and methanol or mixture of ethanol and propanol into a reactor packed with the transition metal-hydroxyl phosphate catalysts to produce benzyl alcohol or ethyl benzyl alcohol by one-pot synthesis through a designed coupling-aromatization reaction.

2. The method according to claim 1, wherein in the step (1), the concentration of the transition metals aqueous solution is 0.08 g/mL-0.75 g/mL; the concentration of the transition metals alcohol solution is 0.08-0.3 g/mL.

3. The method according to claim 1, wherein corresponding soluble salts of transition metals are one or mixture of more than one of chloride, nitrate, levulinate, sulfate and acetate; the alcohol solvent is selected from methanol and/or ethanol.

4. The method according to claim 3, wherein in the step (4), the concentration of hydrogen atmosphere is one of 5-20 vol % H.sub.2/N2or H.sub.2/He or H.sub.2/Ar.

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

Description

DETAILED DESCRIPTION

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

(2) The hydroxyl phosphate is represented by HAP-M, wherein

(3) HAP represents hydroxymetallic apatite; and M refers to metal and is one or more of Mg, Ca, Sr, Ba, Pb, etc.

(4) The catalysts are represented by xMetal-HAP-M, wherein
x=weight percent of metal loading in total weight of the catalysts×100.

Embodiment 1

(5) Synthesis of Co-HAP-Ca Catalyst:

(6) (1) HAP-Ca is dried at 120° C. for 2 h in an airflow oven to remove physical adsorption water on its surface;

(7) (2) Catalyst mixture are prepared via an incipient wetness impregnation method via treating the HAP-Ca dried in the step (1) at 25° C. using Co(NO.sub.3).sub.2 aqueous solution prepared in entry 3 in Table 1, and stayed for 2 h;

(8) (3) The obtained mixture after staying in step (2) is then dried at 100° C. for 10 h under the air atmosphere to obtain corresponding catalyst precursors;

(9) (4) The catalyst precursor obtained in the step (3) is further oxidized at 350° C. for 2 h in the air atmosphere, and then subjected reduction treatment at 400° C. for 2 h (10 vol % H.sub.2/N.sub.2) to obtain Co-HAP-Ca, which was denoted as Co-HAP-Ca (entry 3 in Table 1);

(10) (5) The loading of Co can be changed by controlling metal salt concentration and impregnation time, with the preparation method the same as the above steps, corresponding to entries 2, 3, and 4 in Table 1.

(11) The preparation conditions of other catalysts are the same as these in embodiment 1. The corresponding relationship between the sample number and the preparation conditions are shown in Table 1.

(12) TABLE-US-00001 TABLE 1 Corresponding Relationship between Sample Number and Preparation Conditions in Embodiment 1 Loading/ Concentration/ Temperature Entry Catalyst wt % Support Metals Solvent g/mL /° C. 1 HAP-Ca 0 HAP-Ca Cobalt Water 0 400 nitrate 2 0.1Co-HAP-Ca 0.1 HAP-Ca Cobalt Water 0.1 400 nitrate 3 1.6Co-HAP-Ca 1.6 HAP-Ca Cobalt Water 0.75 400 nitrate 4 8.9Co-HAP-Ca 8.9 HAP-Ca Cobalt Water 0.75 400 nitrate 5 1.6Co-HAP-Sr 0.8 HAP-Sr Cobalt Water 0.5 400 nitrate 6 1.6Co-HAP-Mg 0.8 HAP-Mg Cobalt Water 0.5 400 nitrate 7 1.6Co-HAP-Ba 0.8 HAP-Ba Cobalt Water 0.75 400 nitrate 8 1.6Co-HAP-Pb 0.8 HAP-Pb Cobalt Water 0.5 400 nitrate 9 1.6Co-HAP- 0.8 HAP-Ca/Sr Cobalt Water 0.5 400 Ca/Sr nitrate 10 1.6Co-HAP- 0.8 HAP-Ca/Sr/Ba Cobalt Water 0.5 400 Ca/Sr/Ba nitrate 11 1.6Co-HAP-Ca+ 0.8 HAP-Ca Cobalt Water 0.5 400 1.6Ni-HAP-Ca nitrate 12 1.6Co-HAP-Ca 0.8 HAP-Ca Cobalt Water 0.5 400 chloride 13 1.6Co-HAP-Ca 0.8 HAP-Ca Cobalt Water 0.5 400 acetate 14 1.6Ni-HAP-Ca 0.8 HAP-Ca Nickel Water 0.5 500 nitrate 15 0.3Cu-HAP-Ca 0.8 HAP-Ca Copper Water 0.5 400 nitrate 16 0.8Ag-HAP-Ca 0.8 HAP-Ca Silver Water 0.5 400 nitrate 17 0.8ZnO-HAP-Ca 0.8 HAP-Ca Zinc Water 0.5 400 nitrate 18 0.5Co0.5ZnO- 0.8 HAP-Ca Cobalt Water 0.3 400 HAP-Ca nitrate + Nickel nitrate 19 1.6Co-HAP-Ca 0.8 HAP-Ca Cobalt Ethanol 0.3 400 nitrate 20 1.6Co-HAP-Ca 0.8 HAP-Ca Cobalt Methanol 0.3 400 nitrate

Embodiment 2

(13) Synthesis of Co and ZnO-HAP—Ca-Based Catalyst:

(14) (1) HAP-Ca is dried at 120° C. for 2 h in an airflow oven to remove physical adsorption water on its surface;

(15) (2) At 25° C., the Co(NO.sub.3).sub.2 aqueous solution prepared in entry 3 in Table 1 and the Zn(NO.sub.3).sub.2 aqueous solution prepared in entry 17 are mixed at equal volume; and then, an incipient wetness impregnation method is used to treat the HAP-Ca dried in the step (1) to stand for 2 h;

(16) (3) the obtained mixture after staying in step (2) is then dried at 100° C. for 10 h under the air atmosphere to obtain corresponding catalyst precursors;

(17) (4) the catalyst precursor obtained in the step (3) is oxidized at 350° C. for 2 h in the air atmosphere, and then subjected to hydrogen reduction at 450° C. for 2 h (10 vol % H.sub.2/N.sub.2) to obtain Co and ZnO-HAP-Ca catalyst, which is denoted as CoZnO-HAP-Ca (entry 18 in Table 1) catalyst.

Embodiment 3

(18) Several transition metal-hydroxyl phosphate catalyze the conversion of ethanol and methanol to benzyl alcohol.

(19) the coupling and aromatization of ethanol and methanol is conducted in a fix-bed, atmosphere pressure reactor by co-feeding ethanol and methanol. The used catalyst is first packed in the fix-bed reactor with an inner diameter of 8 mm and kept at 300° C. Then, liquid ethanol is fed in a rate of 0.1 mL/h; and methanol liquid is fed in a rate of 0.2 mL/h. After steady, the product distributions are analyzed by an on-line gas chromatography (GC). The corresponding relationship between sample number and catalytic activity is shown in Table 2.

(20) TABLE-US-00002 TABLE 2 Corresponding Relationship between Sample Number and Ethanol and Methanol Conversion and Benzyl Alcohol Selectivity in Embodiment 3 Ethanol Methanol Entry Catalyst conversion conversion Selectivity/% 1 HAP-Ca 18.1 3.2 0.1 2 0.1Co-HAP-Ca 19.3 3.8 3.3 3 1.6Co-HAP-Ca 22.1 5.7 35.2 4 8.9Co-HAP-Ca 25.9 5.5 25.5 5 1.6Co-HAP-Sr 24.9 4.9 29.1 6 1.6Co-HAP-Mg 20.2 3.8 25.8 7 1.6Co-HAP-Ba 26.6 4.2 19.0 8 1.6Co-HAP-Pb 28.6 3.2 12.5 9 1.6Co-HAP-Ca/Sr 25.5 5.5 30.5 10 1.6Co-HAP-Ca/Sr/Ba 25.5 5.6 29.2 11 1.6Co-HAP-Ca + 24.1 5.1 25.0 1.6Ni-HAP-Ca 12 1.6Co-HAP-Ca 20.1 4.8 26.2 13 1.6Co-HAP-Ca 19.8 4.6 25.2 14 1.6Ni-HAP-Ca 22.2 4.3 20.1 15 0.3Cu-HAP-Ca 25.0 7.8 19.8 16 0.8Ag-HAP-Ca 16.0 5.4 20.8 17 0.8ZnO-HAP-Ca 26.2 5.2 32.0 18 0.5Co0.5ZnO-HAP-Ca 20 5.3 34.2 19 1.6Co-HAP-Ca 17.2 4.5 25.5 20 1.6Co-HAP-Ca 22.1 4.5 21.0

Embodiment 4

(21) Effect of the Partial Pressure of Ethanol and Methanol on Selectivity of Benzyl Alcohol with Co-HAP-Ca Catalysts

(22) The coupling and aromatization of ethanol and methanol is conducted in a fix-bed, atmosphere pressure reactor by feeding ethanol and methanol. Reaction conditions are as follows: the catalyst is first packed in the fix-bed reactor with an inner diameter of 8 mm at 1 atm pressure and reaction temperature of 300° C. The total partial pressure of ethanol and methanol is 6 kPa. The relative ratio of ethanol and methanol is adjusted by controlling the flow rate of the ethanol and methanol. After steady, the reaction reactants and products are analyzed by an on-line gas chromatography (GC). Table 3 shows the ethanol and methanol conversion and the selectivity of benzyl alcohol under different partial pressures.

(23) TABLE-US-00003 TABLE 3 Effect of Relative Partial Pressure of Ethanol and Methanol of Embodiment 4 on Selectivity of Benzyl Alcohol Ethanol Methanol Ethanol Methanol (kPa) (kPa) conversion conversion Selectivity/% 6 0 18.1 / 0 4 2 12.5 6.5 10.3 3 3 17.6 6.3 21.6 2 4 22.1 5.7 35.2 1 5 29.6 8.5 35.1

Embodiment 5

(24) Several transition metal-hydroxyl phosphate catalysts are used to catalyze the conversion of ethanol and propanol to ethyl benzyl alcohol.

(25) Ethanol and propanol coupling-aromatization reaction is conducted in a fix-bed, atmosphere pressure reactor by feeding ethanol and propanol as reactants. 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 300° C. Then, ethanol liquid is fed in a rate of 0.1 mL/h; and propanol liquid is fed in a rate of 0.1 mL/h. After steady, the reaction reactants and products are analyzed by an on-line gas chromatography (GC). The corresponding relationship between sample number and catalytic activity is shown in Table 4.

(26) TABLE-US-00004 TABLE 4 Corresponding Relationship between Sample Number and Ethanol and Propanol Conversion and Ethyl Benzyl Alcohol Selectivity in Embodiment 5 Ethanol Propanol Selectivity/ Entry Catalyst conversion/% conversion/% % 1 HAP-Ca 15.1 5.2 0.1 2 0.1Co-HAP-Ca 16.3 5.8 2.3 3 1.6Co-HAP-Ca 18.7 6.7 11.2 4 8.9Co-HAP-Ca 15.7 5.5 8.5 5 1.6Co-HAP-Sr 14.9 4.9 9.1 6 1.6Co-HAP-Mg 13.2 4.8 8.7 7 1.6Co-HAP-Ba 17.1 5.1 7.9 8 1.6Co-HAP-Pb 16.6 4.9 7.5 9 1.6Co-HAP-Ca/Sr 15.5 5.0 9.5 10 1.6Co-HAP-Ca/Sr/Ba 14.9 5.4 10.2 11 1.6Co-HAP-Ca + 15.1 5.1 9.0 1.6Ni-HAP-Ca 12 1.6Co-HAP-Ca 16.1 4.8 6.2 13 1.6Co-HAP-Ca 15.8 4.6 5.2 14 1.6Ni-HAP-Ca 19.2 7.3 8.1 15 0.3Cu-HAP-Ca 20.0 6.8 3.8 16 0.8Ag-HAP-Ca 16.0 5.4 8.8 17 0.8ZnO-HAP-Ca 16.2 5.2 9.0 18 0.5Co0.5ZnO-HAP-Ca 20 5.3 10.2 19 1.6Co-HAP-Ca 17.2 5.5 7.5 20 1.6Co-HAP-Ca 21.1 4.5 9.0

Embodiment 6

(27) Effect of the partial pressure of ethanol and propanol on selectivity of ethyl benzyl alcohol with Co-HAP-Ca catalysts.

(28) Ethanol and propanol coupling-aromatization reaction is conducted in a fix-bed, atmosphere pressure reactor by feeding ethanol and propanol as reactants. Reaction conditions are as follows: the catalyst is first packed in the fix-bed reactor with an inner diameter of 8 mm at normal pressure and reaction temperature of 300° C. The total partial pressure of ethanol and propanol is 6 kPa. The relative ratio of ethanol and propanol is adjusted by controlling the feed flow rate of the ethanol and propanol.

(29) TABLE-US-00005 TABLE 5 Effect of Relative Partial Pressure of Ethanol and Propanol of Embodiment 6 on Selectivity of Ethyl Benzyl Alcohol Ethanol Propanol Ethanol/ Propanol/ conversion/ conversion/ kPa kPa % % Selectivity/% 6 0 18.3 / 0 4 2 12.7 4.2 3.5 3 3 16.6 5.5 8.1 2 4 18.7 6.2 11.2 1 5 30.9 10.3 11.3