METHOD OF CATALYTIC CONVERSION OF CARBOHYDRATES TO LOW-CARBON DIOLS BY USING ALLOY CATALYSTS

Abstract

This invention provides a method for catalytic conversion of carbohydrates to low-carbon diols using alloy catalysts. In the process, carbohydrates as the feedstock are subjected to one-step catalytic conversion to realize the highly efficient and selective production of ethylene glycol etc. under hydrothermal conditions, with an alloy catalyst composed of tin, and a transition metal such as iron, cobalt, nickel, rhodium, ruthenium, palladium, iridium, platinum and copper, or a mixture thereof. The reaction is carried out in water at a temperature range of 120-300 C., with a hydrogen pressure range of 1-13 MPa. Compared with the present petroleum based synthesis technology of ethylene glycol, the method in this invention possesses advantages of using renewable feedstock, high atom economy and environmental friendly. Besides, compared with other technologies using biomass as feedstock to produce ethylene glycol, the alloy catalyst in this invention possesses the advantages of few leaching amount, good hydrothermal stability and easy to recycle.

Claims

1. A method for catalytic conversion of carbohydrates to low-carbon diols using alloy catalysts, wherein carbohydrate as the feedstock subjected to catalytic hydrogenation in high pressure reactor in water; an alloy catalyst is synthesized from at least two kinds of metal precursors; said alloy catalyst is composed of tin and a transition metal selected from iron, cobalt, rhodium, ruthenium, palladium, iridium, platinum and copper, or a mixture thereof; the weight ratio between tin and other metals is in the range of 0.01-100; or, the alloy catalyst is composed of the precursors of tin and other metals before use; the precursors of tin are selected from metallic tin or tin compounds, or a mixture thereof; the precursors of other metals are selected from metallic iron, cobalt, rhodium, ruthenium, palladium, iridium, platinum and copper, or iron, cobalt, rhodium, ruthenium, palladium, iridium, platinum and copper compounds, or a mixture thereof; the alloy is in situ formed from tin and other metals and the weight ratio between tin and other metals is in the range of 0.01-100; a reaction is conducted in sealed high pressure reactor, continuous high pressure reactor or semi continuous high pressure reactor; hydrogen is filled in the reactor before reaction; the reaction is conducted at temperatures higher than 120 C.; the reaction time is no less than 5 minutes or liquid hourly space velocity is not more than 20 h-1; the weight concentration of said alloy catalysts in the reaction system is between 0.1% and 50%; said low-carbon diols are ethylene glycol or 1,2-propylene glycol, or a mixture thereof.

2. According to the method of claim 1, the hydrogen is filled in the reactor before reaction; the initial hydrogen pressure at room temperature is particularly between 1 and 12 MPa; the reaction temperature is higher than 120 C. and the upper limit of temperature is the highest temperature that the thermal decomposition of product do not occur.

3. According to the method of claim 1, the reaction temperature is particularly between 200 and 280 C.; the initial hydrogen pressure at room temperature is particularly between 3 and 7 MPa; with regard to the sealed high pressure reactor, the reaction time is between 0.5 and 5 h; with regard to the continuous high pressure reactor or semi continuous high pressure reactor, the liquid hourly space velocity GWSV is between 0.1 and 50 h.sup.1; the liquid hourly space velocity GWSV represents the ratio of the dry mass of feedstock into the reactor hourly to the mass of catalyst in the reactor.

4. According to the method of claim 1, the alloy catalyst is a non-supported catalyst; the alloy catalyst is a skeletal metal catalyst, in which the metals of alloy compose the skeleton of catalyst; the preferred skeletal catalyst is composed of nickel-tin alloy; the weight ratio between tin and other metals is in the range of 0.1-10; the weight concentration of alloy catalyst in the reaction system is between 1% and 30%.

5. According to the method of claim 1, the weight ratio between tin and other metals in the skeleton alloy catalyst is in the range of 0.5-2; the weight concentration of alloy catalyst in the reaction system is between 2% and 20%.

6. According to the method of claim 1, the alloy catalyst is a supported catalyst; metallic tin and other metals including iron, cobalt, rhodium, ruthenium, palladium, iridium, platinum and copper, or a mixture thereof are supported on a carrier; the carrier is selected from activated carbon, alumina, silica, silicon carbide, zirconia, zinc oxide and titanium dioxide, or a mixture thereof; the weight concentration of alloy in the supported catalyst is between 0.01% and 50 wt %; the weight ratio between tin and other metals in the supported catalyst is in the range of 0.1-10.

7. According to the method of claim 6, the weight concentration of alloy in the supported catalyst is between 1% and 35 wt %; the weight ratio between tin and other metals in the supported catalyst is in the range of 0.5-2.

8. According to the method of claim 1, metallic or compounds of transition metals including iron, cobalt, rhodium, ruthenium, palladium, iridium, platinum and copper, or a mixture thereof are supported on a carrier; the carrier is selected from metallic tin or tin compounds, or a mixture thereof; the weight concentration of transition metals in the catalyst is between 0.01% and 50 wt %; or, metallic tin or tin compounds, or a mixture thereof are supported on a carrier; the carrier is selected from metallic or compounds of transition metals including iron, cobalt, rhodium, ruthenium, palladium, iridium, platinum and copper, or a mixture thereof; the weight concentration of tin in the catalyst is between 0.01% and 50 wt %.

9. According to the method of claim 1, the masses of water and feedstock put into the reactor should ensure that the status of the whole material in the reactor under reaction condition is partially or completely is liquid; carbohydrate is selected from cellulose, starch, hemicellulose, jerusalem artichoke, saccharose, glucose, mannose, fructose, levulan, xylose, arabinose, xylooligosaccharide, erythrose and chitosan, or a mixture thereof.

10. According to the method of claim 1, metallic tin or tin compounds including metallic tin, stannous fluoride, stannous fluoride, stannous bromide, stannous iodide, stannic fluoride, stannic chloride, stannic bromide, stannic iodide, stannic hydroxide, stannous hydroxide, stannous oxide, stannic oxide, stannous mono-sulphate, stannic acetate, stannous oxalate, sodium stannate, potassium stannate, calcium stannate, tin phosphide and stannous pyrophosphate, or a mixture thereof; metallic or compounds of transition metals including metallic iron, metallic cobalt, metallic rhodium, metallic ruthenium, metallic palladium, metallic iridium, metallic platinum, metallic copper, skeletal iron (Raney iron), skeletal cobalt (Raney cobalt), skeletal copper (Raney copper), ferric nitrate, cobalt nitrate, ruthenium nitrosyl nitrate, rhodium nitrate, palladium nitrate, iridium nitrate, platinum nitrate, copper nitrate, ferric chloride, cobalt chloride, ruthenium chloride, rhodium chloride, palladium chloride, iridium chloride, platinum chloride, copper chloride, ferric oxide, ferroferric oxide, ferrous oxide, iron sulfate, cobalt(II) oxide, cobalt sesquioxide, cobaltosic oxide, cobaltous sulfate, nickel sulfate, copper oxide and copper sulfate, or a mixture thereof.

Description

DESCRIPTION OF THE DRAWING

[0032] FIG. 1 XRD pattern of the skeletal NiSn alloy catalyst prepared by hydrothermal treatment

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0033] For further illustrating the invention, detailing experiments are described below. It should be noted that the following examples are intended to describe but not to limit the invention.

Example 1

[0034] The preparation of supported alloy catalysts: the metal salts of tin and iron, cobalt, nickel, rhodium, ruthenium, palladium, iridium and platinum were supported on a carrier by an incipient impregnation method. Water is used as the solvent to dissolve metal salts and the carrier is selected from activated carbon, alumina, silica, silicon carbide, zirconia, zinc oxide and titanium dioxide, or a mixture thereof. The catalyst was dried overnight at 120 C., and then reduced at 300 C. for 2 h. Finally, the catalyst should be passivated under 1% O.sub.2/N.sub.2 (V/V) for 4 h before use.

Example 2

[0035] The preparation of nickel supported on stannic oxide catalyst: 1.8 g Ni(NO.sub.3).sub.2.6H.sub.2O were dissolved in 20 ml water, then 1.5 g SnO.sub.2 was added to the prepared solution followed by stirring at 25 C. for 12 h until the complete evaporation of water. The catalyst was dried at 120 C. for 8 h, and then calcined at 300 C. for 2 h under N.sub.2, and finally reduced at 300 C. for 2 h under H.sub.2.

Example 3

[0036] The preparation of nickel supported on ferric oxide catalyst: 0.9 g SnCl.sub.4.5H.sub.2O was dissolved in 20 ml water, then 1.5 g Fe.sub.2O.sub.3 was added to the prepared solution followed by stirring at 25 C. for 12 h until the complete evaporation of water. The catalyst was dried at 120 C. for 8 h, and then calcined at 300 C. for 2 h under N.sub.2, and finally reduced at 300 C. for 2 h under H.sub.2.

Example 4

[0037] The preparation of hydrogenation catalyst: platinum chloride, palladium chloride, ruthenium chloride, rhodium chloride, iridium chloride, nickel nitrate, ferric nitrate, cobalt nitrate and copper nitrate were dissolved in water, respectively. The prepared different metal salts solutions were impregnated on a carrier by an incipient impregnation method, respectively. The catalyst was dried at 120 C. overnight.

[0038] For the supported precious catalysts of platinum, palladium, ruthenium, rhodium, iridium, etc., the catalyst were reduced at 250 C. for 2 h, followed by passivated under 1% O.sub.2/N.sub.2 (V/V) for 4 h before use. For the supported non-precious catalysts of nickel, iron, cobalt, copper, etc., the catalyst were reduced at 450 C. for 2 h, followed by passivated under 1% O.sub.2/N.sub.2 (V/V) for 4 h before use.

Example 5

[0039] The in situ preparation of the alloy catalyst: The combination of metallic tin or tin compounds, or a mixture thereof and metallic hydrogenation catalyst or skeletal catalyst was put into the reactor. The reaction conditions are the same as Example 7, and the alloy catalyst is in situ formed.

Example 6

[0040] The preparation of skeletal alloy catalyst (hydrothermal treatment): 0.6 g metallic tin, 1.0 g skeletal nickel catalyst (Raney Ni) and 10-100 mL water were put into the kettle. The hydrothermal treatment was carried out under 7 MPa H.sub.2 at 250 C. for 3 h. After the treatment, the obtained catalyst was dried overnight at 120 C. before use. FIG. 1 was the XRD spectra of the obtained NiSn alloy catalyst prepared by hydrothermal treatment. The XRD results showed that the formation of NiSn alloy after hydrothermal treatment.

Example 7

[0041] Catalytic conversion experiment: 0.25 g carbohydrate, a designed amount of composite catalyst and 25 ml water were put into the 75 ml autoclave. After flushing with hydrogen for three times, the reactor was pressurized with 5 MPa H.sub.2, and then the temperature was increased to a designed temperature and kept for 30-240 min. After the reaction, the autoclave was cooled to room temperature. The liquid products were separated from catalysts by centrifugation. The liquid products were analyzed by high performance liquid chromatography, and only the yields of ethylene glycol, hexitol (sorbitol and mannitol) and 1,2-propylene glycol were calculated.

Example 8

[0042] Results of cellulose conversion to polyols over supported alloy catalysts. The alloy catalyst was composed of two components, in which one component was metallic tin and the other was transition metals. The loadings of metallic tin and transition metals were 3% and 5%, respectively. The reaction conditions are the same as Example 7.

TABLE-US-00001 TABLE 1 Results of cellulose conversion to polyols over supported alloy catalysts (supported alloy catalyst 0.1 g, reaction temperature 245 C., reaction time 95 min) Conversion Yield of Yield of of ethylene 1,2-propylene Yield of Catalyst cellulose/% glycol/% glycol/%) hexitol/% Ni/AC 100 7.3 6.6 29.4 Ru/AC 100 8.1 5.7 19.2 Pt/AC 98 5.6 5.3 22.9 Ir/AC 90 7.8 11.2 20.3 NiSn/AC 100 38.7 9.5 6.1 RuSn/AC 100 39.8 9.7 5.4 PtSn/AC 100 43.6 7.5 1.5 IrSn/AC 100 54.4 13.2 4.6. Ni/SnO.sub.2 100 45.6 10.1 5.2 Sn/Fe.sub.2O.sub.3 100 26.8 11.9 6.1

[0043] As shown in Table 1, supported alloy catalysts promoted the production of ethylene glycol. Comparing the yields of ethylene glycol and hexitol over alloy catalysts and transition metals hydrogenation catalyst, the formation of alloy improved the yield of ethylene glycol, but the yield of hexitol decreased.

Example 9

[0044] Results of cellulose conversion to polyols over non-supported alloy catalyst. The alloy catalyst was composed of two components, in which one component was metallic tin and the other was transition metals. The reaction conditions are the same as Example 7.

TABLE-US-00002 TABLE 2 Results of cellulose conversion to polyols over non-supported alloy catalysts (non-supported alloy catalyst 0.05 g, the mass ratio of tin to nickel, copper and cobalt was 1:3, 1:5 and 1:2.5 respectively, reaction temperature 245 C., reaction time 95 min) Conversion Yield of Yield of of ethylene 1,2-propylene Yield of Catalyst cellulose/% glycol/% glycol/% hexitol/% Raney Ni 82 6.4 11.5 20.1 Raney Cu 85 4.3 9.6 27.9 Raney Co 76 5.8 4.5 18.9 Raney NiSn 100 54.5 13.3 4.6 Raney CuSn 100 56.9 10.3 5.9 Raney CoSn 100 50.2 11.3 6.1

[0045] As shown in Table 2, non-supported alloy catalysts promoted the production of ethylene glycol. Comparing the yields of ethylene glycol and hexitol over alloy catalysts and skeletal metals hydrogenation catalyst, the formation of alloy improved the yield of ethylene glycol, but the yield of hexitol decreased.

Example 10

[0046] Catalytic conversion results of different carbohydrates to polyols. RuSn/AC was used as supported alloy catalyst for the conversion of different carbohydrates. The mass ratio of tin to ruthenium was 1:3.5, and the loading of ruthenium was 5%. The reaction conditions are the same as Example 7.

TABLE-US-00003 TABLE 3 Results of catalytic conversion of different carbohydrates to polyols (RuSn/AC 0.1 g, reaction temperature 245 C., reaction time 95 min) Yield of Yield of ethylene 1,2-propylene Yield of Yield of Carbohydrate glycol/% glycol/% glycerol/%) sorbitol/% cellulose 58.7 9.5 1.8 6.1 jerusalem 11.3 24.0 3.5 4.8 artichoke soluble 27.0 19.7 6.4 16.8 starch fructose 17.3 24.2 25 0.8 xylose 49.4 20.9 12 1.5 sucrose 21.8 23.8 22 2.4 glucose 27.3 21.2 20 3.7 sorbitol 2.2 2.9 1.2 87.2 xylitol 2.5 2.4 1.0 92.5 (xylitol) glycerol 3.1 5.0 93

[0047] As shown in Table 3, RuSn/AC showed higher selectivity to ethylene glycol and 1,2-propylene glycol than sorbitol, which indicated that RuSn/AC was active for the CC bond cleavage of carbohydrates bearing unsaturated bonds. The yield of ethylene glycol obtained from cellulose was higher than that form other carbohydrates. The selectivity of ethylene glycol and 1,2-propylene glycol depended on the carbohydrates. The yield of 1,2-propylene glycol would be improved, when the carbohydrates contained fructose or could be isomerized to fructose. However, RuSn/AC showed low activity towards the conversion of sorbitol, and CC bonds of sorbitol could not be selectively cracked to produce ethylene glycol and 1,2-propylene glycol. Similarity, RuSn/AC showed low activity towards the conversion of xylitol and glycerol.

Example 11

[0048] Effect of reaction time. PtSn/AC (0.5% Sn, 5% Pt) was selected as supported alloy catalyst for the investigation of reaction time effect (Table 4). The reaction conditions are the same as Example 7 except for the reaction time.

TABLE-US-00004 TABLE 4 Results of catalytic conversion of cellulose to polyols at different time over PtSn/AC. (PtSn/AC 0.1 g, reaction temperature 245 C.) Conversion Yield of Yield of of ethylene 1,2-propylene Yield of Time/min cellulose/% glycol/% glycol/%) hexitol/% 10 69 29.9 4.5 7.4 20 86 40.6 8.1 7.4 45 94 46.4 8.5 6.7 70 98 50.4 9.0 5.2 95 100 52.3 9.5 6.5 120 100 52.6 8.4 6.4 150 100 50.2 7.3 5.8

[0049] As shown in Table 4, PtSn/AC showed good activity towards the production of ethylene glycol in a certain period. The optimum reaction time was 10 h-2.5 h.

Example 12

[0050] Effect of reaction temperature. IrSn/AC (3.5% Sn, 5% Ir) was selected as supported alloy catalyst for the investigation of reaction temperature effect (Table 5). The reaction conditions are the same as Example 7 except for the reaction temperature.

TABLE-US-00005 TABLE 5 Results of catalytic conversion of cellulose to polyols at different temperature over IrSn/AC (IrSn/AC 0.2 g, reaction time 95 min) Conversion Yield of Yield of of ethylene 1,2-propylene Yield of Temperature/ C. cellulose/% glycol/% glycol/% hexitol/% 215 48 18.7 2.3 11.7 225 67 34.1 2.8 7.2 235 90 52.3 9.5 5.7 245 100 64.7 9.5 6.1 255 100 50.5 9.3 3.8 265 100 46.8 6.8 1.6

[0051] As shown in Table 5, IrSn/AC showed good activity towards the production of ethylene glycol in a certain temperature range. The optimum reaction temperature was 230-260 C.

Example 13

[0052] The effect of mass ratio of Sn to Ir. IrSn/AC was selected as supported alloy catalyst for the investigation of mass ratio of Sn to Ir. The reaction conditions are the same as Example 7.

TABLE-US-00006 TABLE 6 The effect of mass ratio of Sn to Ir on the catalytic conversion of cellulose to polyols (IrSn/AC 0.1 g, reaction temperature 245 C., reaction time 95 min) Conversion Yield of Yield of of ethylene 1,2-propylene Yield of Sn/Ir cellulose/%) glycol/% glycol/%) hexitol/% 3.2 100 46.4 10.2 5.1 1.8 100 53.6 9.2 4.9 1.2 100 58.6 9.5 6.5 0.6 100 51.6 6.3 8.9 0.3 100 40.3 7.8 11.2

[0053] As shown in Table 6, IrSn/AC showed good activity towards the production of ethylene glycol in a certain range of mass ratio of Sn to Ir. The optimum mass ratio was 0.6-1.8.

Example 14

[0054] The effect of LHSV. 5% Ir4% Sn/AC was selected as supported alloy catalyst for the investigation of the effect of LHSV. The reaction conditions are the same as Example 7.

TABLE-US-00007 TABLE 7 The effect of LHSV on the catalytic conversion of xylose to polyols (IrSn/AC 5 g, concentration of xylose aqueous solution 20 wt %, reaction temperature 245 C.) Yield of Yield of Conversion ethylene 1,2-propylene Yield of LHSV/h.sup.1 of xylose/% glycol/% glycol/%) hexitol/% 0.2 100 36.4 11.2 6.1 0.5 100 41.6 14.5 4.9 0.8 100 45.7 18.2 3.2 1.1 100 39.2 13.4 7.9 1.7 100 31.3 7.8 11.2

[0055] As shown in Table 7, IrSn/AC showed good activity towards the production of ethylene glycol and 1,2-propylene glycol in a certain LHSV range. The optimum LHSV was 0.8 h.sup.1.

Example 15

[0056] The investigation and comparison of the stability of different alloy catalysts. Raney NiSn, 5% Ni3% Sn/AC and 5% Ir3% Sn/AC were selected as alloy catalysts for the investigation of catalysts stability. The reaction conditions are the same as Example 7.

TABLE-US-00008 TABLE 8 The investigation and comparison of the stability of alloy catalysts. (Raney Ni 0.08 g, NiSn/AC 0.1 g, reaction temperature 245 C., reaction time 95 min) Yield of Yield of Number of ethylene 1,2-propylene Yield of Catalyst usage glycol/% glycol/% hexitol/% Raney NiSn 1 60.4 13.2 4.6. Raney NiSn 2 59.8 10.9 4.2 Raney NiSn 3 54.9 11.1 5.8 Raney NiSn 4 53.7 13.6 2.9 NiSn/AC 1 38.7 9.5 6.1 NiSn/AC 2 28.5 8.2 5.4 NiSn/AC 3 20.3 6.5 4.5 NiSn/AC 4 14.4 4.2 3.1 IrSn/AC 1 54.4 13.2 4.6 IrSn/AC 2 52.3 13.0 4.0 IrSn/AC 4 50.1 12.0 4.7

[0057] As shown in Table 8, Raney NiSn showed good activity towards the production of ethylene glycol in the first four cycles. ICP analysis results of the aqueous solution after every recycle showed that the concentration of nickel and tin was lower than 1 ppm, which indicated that the leaching amount of active ingredient of Raney NiSn was few. IrSn/AC also showed good activity and stability in the conversion of cellulose to ethylene glycol. However, the catalytic activity and stability of NiSn/AC were worse than that of Raney NiSn. Skeletal NiSn alloy catalyst (Raney NiSn) showed superior catalytic activity.

[0058] The alloy catalyst in this invention could catalyze the highly efficient conversion of carbohydrates to ethylene glycol and 1,2-propylene glycol. The method in this invention possesses advantages of easy operation and low cost. Besides, the alloy catalysts provided by this method possess advantages of few leaching amount, good hydrothermal stability and easy to recycle.