CN101613253B - Catalytic cracking method for sugar and sugar alcohol - Google Patents
Catalytic cracking method for sugar and sugar alcohol Download PDFInfo
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- CN101613253B CN101613253B CN200810011993A CN200810011993A CN101613253B CN 101613253 B CN101613253 B CN 101613253B CN 200810011993 A CN200810011993 A CN 200810011993A CN 200810011993 A CN200810011993 A CN 200810011993A CN 101613253 B CN101613253 B CN 101613253B
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Abstract
The invention relates to a method for preparing low-carbon alcohol through the catalytic cracking of sugar and sugar alcohol, which comprises the steps: under the action of an Ni-based catalyst, taking polycarbon sugar such as glucose, fruit sugar, xylose, sorbierite, mannite and xylitol, and water solution of various carbon sugar and sugar alcohol as raw materials, and cracking the raw materials into low-carbon alcohol of C3 or below C3 (particularly glycol and 1,2-propanediol) in a high selectivity mode through hydrogenation and dehydration processes. The conversion rate of the raw materials reaches over 95 percent. The yield of the glycol and the 1,2-propanediol in the low-carbon alcohol reaches over 50 percent. The method has the advantages of high efficiency, mild conditions, and high selectivity of the low-carbon alcohol.
Description
Technical field
The present invention relates to the sugar in biomass source and the catalytic pyrolysis of sugar alcohol and prepare C
2And C
3The method of low-carbon alcohol, especially a kind of sugar and sugar alcohol catalytic pyrolysis generate terepthaloyl moietie and 1, the method for 2-Ucar 35.
Background technology
Low-carbon alcohol such as ethanol, terepthaloyl moietie, propyl alcohol, Ucar 35 and USP Kosher are important petrochemical materialss, mainly are used as energy liquid fuel, organic solvent and synthetic intermediate; It also is the key chemicals of synthesizing polyester.Terepthaloyl moietie also can be used as industries such as frostproofer, lubricant, softening agent, tensio-active agent, coating, soup, brake fluid and printing ink; Ucar 35 can be widely used in food, medicine and the cosmetic industry, uses as moisture adsorbent, antifreezing agent, lubricant and solvent, also can be used as tobacco moistening agent, mould inhibitor and fruit ripener etc.
For a long time, the production of terepthaloyl moietie and Ucar 35 mainly is that the employing petroleum resources are the technological line of raw material, is raw material with ethene or propylene promptly, obtains epoxy compounds through epoxidation, and epoxy compounds can obtain terepthaloyl moietie or Ucar 35 through hydration then.Though these synthetic routes are ripe, have following limitation: (1) this technological line is that to adopt fossil resources such as ethene and propylene be raw material, and reserves are restricted and recyclable regenerative not.(2) production process need be passed through catalytic processs such as epoxidation, hydration, and technical difficulty is big, and route is long, and efficient is low.Develop the new technology path that non-fossil resource prepares low-carbon alcohol such as terepthaloyl moietie and Ucar 35, have great importance and application prospect.
Sugar is the important component part of glucide in the nature biotechnology matter with sugar alcohol, can cyclic regeneration through photosynthesis, and content is abundant, and it is extensive to distribute at occurring in nature; Adopt catalytic pyrolysis to be converted into C with important use
2, C
3Etc. the method for low-carbon alcohol, be a Sustainable development, competitive technological line; Especially synthesizing glycol and Ucar 35 technology can effectively improve the level of resources utilization, realizes the application of atom economy property.
Up to the present, the method that the research that directly transforms through biomass material and industrial application adopt fermentation mostly, and the research of catalytic pyrolysis report seldom, especially with prepare terepthaloyl moietie and Ucar 35 be target product research still less.Though it is proven technique in the industry that carbohydrate fermentation prepares the method for alcohol fuel, yield is low, pollutes greatly, and cost is high.USP 6,291,725 have reported the scission reaction of the Ru/C catalyst Xylitol aqueous solution, at 9.3Mpa, under 230 ℃, transformation efficiency is 53.2%; This Technology Need adopts noble metal catalyst, need in reaction system, add a large amount of alkali.USP 6,841,085,6,677; 385 and 6,479,713 have reported the research of Ni-Re cracking catalyst sorbyl alcohol, in the presence of alkali; Under 220 ℃, 4.0-12.0MPa, the transformation efficiency of sorbyl alcohol is 50-60%, glycol selectivity 10%-15%, and the Ucar 35 selectivity is 15-30%.Cracking condition is harsh, and efficient is low, and transformation efficiency and selectivity are not high.
Summary of the invention
The object of the present invention is to provide the novel method of a kind of sugar and sugar alcohol catalytic pyrolysis; Under catalyst action; The efficient cracking of the aqueous solution of the sugar in biomass source and sugar alcohol generates low-carbon alcohol, especially terepthaloyl moietie and 1,2-Ucar 35; This method efficient is high, mild condition, and has very high low-carbon alcohol selectivity.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
The catalytic cracking method of a kind of sugar and sugar alcohol, under the catalyst based effect of Ni, the aqueous solution of sugar and sugar alcohol, through hydrogenation and dehydration, highly selective hydrocracking generates carbon three or the low-carbon alcohol of carbon below three; Terepthaloyl moietie and 1 particularly, the 2-Ucar 35.
Selected sugar and sugar alcohol are selected from the aqueous solution of many carbon sugar such as glucose, fructose, wood sugar, sorbyl alcohol, N.F,USP MANNITOL and Xylitol and sugar alcohol compound, and the concentration of sugar or sugar alcohol is 1.0%-99wt%, and preferred values is 10-80%, and optimum value is 10-50%.
Form by active ingredient, auxiliary agent and carrier according to catalyst for cracking of the present invention, adopt the carrying method preparation.
Main active component is the Ni compound, and content is the 1-30% (in metal Ni) of catalyst quality, and preferable mass content is 5-20% (in metal Ni);
The auxiliary agent of catalyzer comprises one or more of Mo, Sn, Mg, Zn, Ce, Cu, Al, Zr, and add-on is the 0.1%-15.0% of catalyst quality, and preferable add-on is the 0.2-8.0% of catalyst quality;
In above-mentioned catalyzer, need to add appropriate carriers.Heterogeneous catalytic reaction is carried out in solid catalyst surface, and suitable carriers can effectively increase the long-pending and proper pore structure of surface availability of catalyst, improves the thermostability of amorphous alloy catalyst, can also increase the relative number in active site.The carrier of catalyzer selects molecular sieve or gac.Wherein, molecular sieve comprises A type molecular sieve, X type molecular sieve, Y zeolite, β-molecular sieve, ZSM-5, ZSM-22, MCM-41, SBA-15 molecular sieve;
Catalyzer adopts immersion process for preparing, and the soluble salt solution of active ingredient and auxiliary agent is loaded on the carrier, after the drying, carries out calcination process under under nitrogen protection, passing through 200-600 ℃, afterwards to catalyst reduction.
According to catalyst consumption of the present invention is the 1-15% of reaction system quality, and preferable consumption is the 3-10% of reaction system quality.Temperature of reaction is 150-300 ℃, and preferable temperature of reaction is 180-250 ℃; Reaction pressure is 2.0-20.0MPa, and preferable reaction pressure is 3.0-7.0MPa; Reaction times is 3-20 hour, and the preferable reaction times is 5-10 hour.
Prepare the method for low-carbon alcohol according to of the present invention by sugar and sugar alcohol hydrogenation cracking, feed stock conversion is for reaching more than 95%.Primary product is for generating C
2And C
3Etc. low-carbon alcohol, the yield of low-carbon alcohol reaches more than 75%, terepthaloyl moietie and 1 particularly, and the 2-Ucar 35, yield is more than 50%.
The present invention has following advantage:
1. what the prepared product of the present invention adopted is non-petroleum path, can effectively alleviate the anxiety of existing petroleum resources.
2. the catalyzer of the usefulness of producing is a base metal, and cost is low, and is cheap, has high catalytic activity and selectivity simultaneously.
Embodiment
Through embodiment the present invention is detailed below:
Embodiment 1
Take by weighing nickelous nitrate and cerous nitrate solution (Ni: Ce=5: 2, mass ratio), add dry back gac (charge capacity of Ni is 8% (total catalyst weight)), dipping 24h, dry 12h.Under nitrogen protection, roasting is 5 hours in the silica tube then.
Embodiment 2
Catalyzer 2-11 prepares process and adopts the method for embodiment 1 to carry out, and just changes different metal component and mass ratio and different carriers.See table 1 for details.
Table 1
Numbering | Catalyst metal components | Mass ratio | Carrier |
1 | Ni-Ce | 5∶2 | Gac |
2 | Ni-Mo | 8∶1 | Activated carbon |
3 | Ni-Sn | 8∶3 | Gac |
4 | Ni-Mg | 8∶5 | CaA |
5 | Ni-Zn | 8∶1 | NaX |
6 | Ni-Cu | 10∶1 | SBA-15 |
7 | Ni-Al | 9∶1 | NaY |
8 | Ni-Zr | 25∶1 | Hβ |
9 | Ni-Cu-Zn | 8.5∶1∶1 | ZSM-5 |
10 | Ni-Zn-Ce | 9∶3∶2.5 | MCM-41 |
11 | Ni-Cu-Zn-Zr | 8∶1;1∶1 | Gac |
The catalytic cracking reaction of embodiment 3 Xylitols
The 200g 30% Xylitol aqueous solution and 10g catalyzer are transferred in the autoclave.After displaced air 3-5 time, be heated to 200 ℃, charge into the hydrogen of 5MPa pressure then, stir fast, the reaction beginning.React after 6 hours, stop to stir, cool to room temperature, lay down hydrogen.Sampling analysis.Xylitol quantitatively through efficient liquid phase chromatographic analysis, terepthaloyl moietie and Ucar 35 quantitative through gas chromatographic analysis, the result sees table 2.
Table 2
The catalyzer numbering | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
1 | 95 | 28 | 48 |
2 | 32 | 5 | 9 |
4 | 59 | 22 | 31 |
5 | 72 | 27 | 37 |
7 | 81 | 28 | 49 |
8 | 70 | 18 | 30 |
9 | 54 | 10 | 17 |
11 | 84 | 31 | 50 |
The catalytic cracking reaction of embodiment 4 Xylitols under the differential responses condition
The 200g Xylitol aqueous solution and catalyzer 1 are transferred in the autoclave.After displaced air 3-5 time, be heated to assigned temperature, charge into the hydrogen of specified pressure then, other processes are with embodiment 3.The result sees table 3.
Table 3
Catalyst levels (%) | Reaction density (wt%) | Reaction pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
3 | 15 | 3 | 200 | 6 | 85 | 25 | 40 |
7 | 15 | 5 | 220 | 8 | 98 | 20 | 41 |
3 | 30 | 3 | 150 | 8 | 68 | 19 | 34 |
5 | 30 | 4 | 180 | 8 | 83 | 24 | 42 |
8 | 30 | 5 | 200 | 6 | 95 | 28 | 48 |
10 | 30 | 6 | 220 | 4 | 92 | 25 | 46 |
10 | 30 | 7 | 250 | 4 | 99 | 18 | 33 |
8 | 50 | 5 | 180 | 4 | 65 | 17 | 32 |
10 | 50 | 6 | 200 | 8 | 73 | 20 | 37 |
8 | 80 | 5 | 200 | 8 | 52 | 15 | 26 |
The scission reaction of embodiment 5 sorbyl alcohols under different catalysts
200g 30% sorbitol aqueous solution and catalyzer are transferred in the autoclave.After displaced air 3-5 time, be heated to 200 ℃, charge into the hydrogen of 5MPa pressure then, stir fast, the reaction beginning.React after 6 hours, stop to stir, cool to room temperature, lay down hydrogen.Sampling analysis.Sorbyl alcohol quantitatively through efficient liquid phase chromatographic analysis, terepthaloyl moietie and Ucar 35 quantitative through gas chromatographic analysis, the result sees table 4.
Table 4
The catalyzer numbering | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
1 | 99 | 11 | 33 |
3 | 34 | 3 | 7 |
4 | 58 | 7 | 18 |
6 | 53 | 5 | 14 |
7 | 80 | 8 | 25 |
9 | 53 | 4 | 11 |
10 | 49 | 4 | 13 |
11 | 85 | 9 | 29 |
The catalytic cracking reaction of embodiment 6 sorbyl alcohols under the differential responses condition
30% sorbitol aqueous solution 200g and 10g catalyzer 1 are transferred in the autoclave.After displaced air 3-5 time, be heated to assigned temperature, charge into the hydrogen of specified pressure then, other processes are with embodiment 5.The result sees table 5.
Table 5
Catalyst levels (%) | Reaction density (wt%) | Reaction pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
3 | 15 | 3 | 200 | 6 | 87 | 10 | 28 |
7 | 15 | 5 | 220 | 8 | 99 | 7 | 22 |
3 | 30 | 3 | 150 | 8 | 59 | 6 | 19 |
5 | 30 | 4 | 180 | 8 | 84 | 9 | 27 |
8 | 30 | 5 | 200 | 6 | 99 | 11 | 33 |
10 | 30 | 6 | 220 | 4 | 99 | 8 | 25 |
10 | 30 | 7 | 250 | 4 | 99 | 6 | 21 |
8 | 50 | 5 | 180 | 4 | 58 | 6 | 19 |
10 | 50 | 6 | 200 | 8 | 73 | 9 | 24 |
8 | 80 | 5 | 200 | 8 | 52 | 7 | 18 |
The catalytic cracking reaction of embodiment 7 N.F,USP MANNITOL
200g 15% Osmitrol and 10g catalyzer are transferred in the autoclave.After displaced air 3-5 time, be heated to assigned temperature, charge into the hydrogen of specified pressure then, stir fast, the reaction beginning.React after 6 hours, stop to stir, cool to room temperature, lay down hydrogen.Sampling analysis.N.F,USP MANNITOL quantitatively through efficient liquid phase chromatographic analysis, terepthaloyl moietie and Ucar 35 quantitative through gas chromatographic analysis, the result sees table 6.
Table 6
The catalyzer numbering | Reaction pressure (MPa) | Temperature of reaction (℃) | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
2 | 3 | 150 | 33 | 3 | 11 |
5 | 4 | 180 | 90 | 9 | 19 |
7 | 5 | 200 | 85 | 10 | 19 |
9 | 5 | 220 | 90 | 7 | 12 |
11 | 6 | 200 | 95 | 11 | 21 |
The hydrocracking of embodiment 8 glucose
200g 30% D/W and 10g catalyzer are transferred in the autoclave.Reaction conditions is that temperature is 200 ℃, and hydrogen pressure is 5MPa, reacts 6 hours.Glucose and macromolecule product quantitatively through efficient liquid phase chromatographic analysis, terepthaloyl moietie and Ucar 35 quantitative through gas chromatographic analysis, the result sees table 7.
Table 7
The catalyzer numbering | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
1 | 97 | 11 | 25 |
4 | 62 | 7 | 19 |
6 | 65 | 5 | 14 |
8 | 70 | 9 | 27 |
11 | 96 | 10 | 29 |
The hydrocracking of embodiment 9 fructose
200g 30% fructose water solution and 10g catalyzer are transferred in the autoclave.Reaction conditions is that temperature is 200 ℃, and hydrogen pressure is 5MPa, reacts 6 hours.Fructose and macromolecule product quantitatively through efficient liquid phase chromatographic analysis, terepthaloyl moietie and Ucar 35 quantitative through gas chromatographic analysis, the result sees table 8.
Table 8
The catalyzer numbering | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
1 | 97 | 13 | 29 |
4 | 63 | 7 | 22 |
7 | 96 | 13 | 30 |
8 | 71 | 9 | 27 |
9 | 43 | 6 | 13 |
The hydrocracking of embodiment 10 wood sugars
The 200g 30% wood sugar aqueous solution and 10g catalyzer are transferred in the autoclave.Reaction conditions is that temperature is 200 ℃, and hydrogen pressure is 5MPa, reacts 6 hours.Wood sugar and macromolecule product quantitatively through efficient liquid phase chromatographic analysis, terepthaloyl moietie and Ucar 35 quantitative through gas chromatographic analysis, the result sees table 9.
Table 9
The catalyzer numbering | Transformation efficiency (%) | Terepthaloyl moietie yield (%) | 1,2-Ucar 35 yield (%) |
1 | 98 | 23 | 36 |
2 | 32 | 6 | 9 |
5 | 75 | 24 | 36 |
9 | 54 | 10 | 19 |
11 | 85 | 21 | 33 |
Claims (8)
1. the catalytic cracking method of sugar and sugar alcohol, it is characterized in that: under the catalyst based effect of Ni, the aqueous solution hydrocracking of sugar and sugar alcohol generates carbon three or the low-carbon alcohol of carbon below three; Temperature of reaction is 150-300 ℃, and the reactive hydrogen atmospheric pressure is 2.0-20.0MPa, and the reaction times is 3-20 hour;
Said catalyzer is made up of active ingredient, auxiliary agent and carrier, adopts the carrying method preparation, and main active component is the Ni compound, and in metal Ni, content is the 1-30% of catalyst quality; Auxiliary agent is one or more of Mo, Sn, Mg, Zn, Ce, Cu, Al, Zr, and add-on is the 0.1%-15.0% of catalyst quality; The carrier of catalyzer is molecular sieve or gac;
Described sugar and sugar alcohol are the sugar and the sugar alcohol in biomass source, and it is the aqueous solution of glucose, fructose, wood sugar, sorbyl alcohol, N.F,USP MANNITOL and/or Xylitol, and the concentration of sugar or sugar alcohol is 1.0wt%-99wt%, and said low-carbon alcohol is C
2And/or C
3Low-carbon alcohol.
2. according to the described method of claim 1, it is characterized in that: the concentration of sugar or sugar alcohol is 10-80%, and said low-carbon alcohol is terepthaloyl moietie and/or 1, the 2-Ucar 35.
3. according to the described method of claim 1, it is characterized in that: the concentration of sugar or sugar alcohol is 10-50%.
4. according to the described method of claim 1, it is characterized in that: in metal Ni, the mass content of catalyst activity component is 5-20%; Said promoter addition is the 0.2-8.0% of catalyst quality.
5. according to the described method of claim 1, it is characterized in that: said molecular sieve is A type molecular sieve, X type molecular sieve, Y zeolite, β-molecular sieve, ZSM-5, MCM-41, SBA-15 molecular sieve.
6. according to the described method of claim 1; It is characterized in that: said catalyzer adopts immersion process for preparing, the soluble salt solution of active ingredient and auxiliary agent is loaded on the carrier, after the drying; Under nitrogen protection, under 200-600 ℃, carry out calcination process, afterwards to catalyst reduction.
7. according to the described method of claim 1, it is characterized in that: catalyst consumption is the 1-15% of reaction system quality; Temperature of reaction is 180-250 ℃; Reaction pressure is 3.0-7.0MPa; Reaction times is 5-10 hour.
8. according to the described method of claim 1, it is characterized in that: catalyst consumption is the 3-10% of reaction system quality.
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