CN101613253A - The catalytic cracking method of a kind of sugar and sugar alcohol - Google Patents
The catalytic cracking method of a kind of sugar and sugar alcohol Download PDFInfo
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- CN101613253A CN101613253A CN200810011993A CN200810011993A CN101613253A CN 101613253 A CN101613253 A CN 101613253A CN 200810011993 A CN200810011993 A CN 200810011993A CN 200810011993 A CN200810011993 A CN 200810011993A CN 101613253 A CN101613253 A CN 101613253A
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Abstract
The present invention relates to the method that a kind of sugar and sugar alcohol catalytic pyrolysis prepare low-carbon alcohol, promptly under the catalyst based effect of Ni, with many carbon sugar such as glucose, fructose, wood sugar, sorbyl alcohol, N.F,USP MANNITOL, Xylitol and sugar alcohol aqueous solution is raw material, by hydrogenation and dehydration, highly selective is cracked into carbon three or the low-carbon alcohol of carbon below three, ethylene glycol and 1 particularly, the 2-propylene glycol.Conversion of raw material reaches more than 95%.Ethylene glycol and 1 in the low-carbon alcohol, the yield of 2-propylene glycol reaches more than 50%.Method efficient height, the mild condition that the present invention relates to, and have very high low-carbon alcohol selectivity.
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 ethylene glycol and 1, the method for 2-propylene glycol.
Background technology
Low-carbon alcohol such as ethanol, ethylene glycol, propyl alcohol, propylene glycol and glycerol 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.Ethylene glycol also can be used as industries such as frostproofer, lubricant, softening agent, tensio-active agent, coating, soup, brake fluid and printing ink; Propylene glycol 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 ethylene glycol and propylene glycol 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 ethylene glycol or propylene glycol 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 ethylene glycol and propylene glycol, have great importance and application prospect.
Sugar and sugar alcohol are the important component parts of carbohydrate in the nature biotechnology matter, can cyclic regeneration by photosynthesis, and content enriches, and is widely distributed 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 propylene glycol technology can effectively improve the level of resources utilization, realize the application of atom economy.
Up to the present, the method that research that directly transforms by biomass material and industrial application adopt fermentation mostly, and the research of catalytic pyrolysis report seldom, especially with preparation ethylene glycol and propylene glycol be target product research still less.Though it is industrial proven technique that carbohydrate fermentation prepares the method for alcohol fuel, yield is low, pollutes greatly the cost height.United States Patent (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 add a large amount of alkali in reaction system.United States Patent (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 propylene glycol selectivity is 15-30%.The cracking condition harshness, 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 ethylene glycol and 1, the 2-propylene glycol, this method efficient height, mild condition, and have very high low-carbon alcohol selectivity.
For achieving the above object, the technical solution used in the present invention 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, by hydrogenation and dehydration, highly selective hydrocracking generates carbon three or the low-carbon alcohol of carbon below three; Ethylene glycol and 1 particularly, the 2-propylene glycol.
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 centre.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 200-600 ℃ under nitrogen protection, 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%, ethylene glycol and 1 particularly, and the 2-propylene glycol, 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
Below by embodiment in detail the present invention is described in detail:
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 preparation process 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 by efficient liquid phase chromatographic analysis, ethylene glycol and propylene glycol quantitatively by gas chromatographic analysis, the results are shown in Table 2.
Table 2
| The catalyzer numbering | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 results are shown in Table 3.
Table 3
| Catalyst levels (%) | Reaction density (wt%) | Reaction pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 by efficient liquid phase chromatographic analysis, ethylene glycol and propylene glycol quantitatively by gas chromatographic analysis, the results are shown in Table 4.
Table 4
| The catalyzer numbering | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 results are shown in Table 5.
Table 5
| Catalyst levels (%) | Reaction density (wt%) | Reaction pressure (MPa) | Temperature of reaction (℃) | Reaction times (h) | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 by efficient liquid phase chromatographic analysis, ethylene glycol and propylene glycol quantitatively by gas chromatographic analysis, the results are shown in Table 6.
Table 6
| The catalyzer numbering | Reaction pressure (MPa) | Temperature of reaction (℃) | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 by efficient liquid phase chromatographic analysis, ethylene glycol and propylene glycol quantitatively by gas chromatographic analysis, the results are shown in Table 7.
Table 7
| The catalyzer numbering | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 by efficient liquid phase chromatographic analysis, ethylene glycol and propylene glycol quantitatively by gas chromatographic analysis, the results are shown in Table 8.
Table 8
| The catalyzer numbering | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol 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 by efficient liquid phase chromatographic analysis, ethylene glycol and propylene glycol quantitatively by gas chromatographic analysis, the results are shown in Table 9.
Table 9
| The catalyzer numbering | Transformation efficiency (%) | Ethylene glycol yield (%) | 1,2-propylene glycol yield (%) |
| ??1 | ??98 | ??23 | ??36 |
| ??2 | ??32 | ??6 | ??9 |
| ??5 | ??75 | ??24 | ??36 |
| ??9 | ??54 | ??10 | ??19 |
| ??11 | ??85 | ??21 | ??33 |
Claims (10)
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.
2. in accordance with the method for claim 1, it is characterized in that: described sugar and sugar alcohol are the sugar and the sugar alcohol in biomass source, it can be 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 1.0%-99wt%, and described low-carbon alcohol is C
2And/or C
3Low-carbon alcohol.
3. in accordance with the method for claim 2, it is characterized in that: the concentration of sugar or sugar alcohol is 10-80%, and described low-carbon alcohol is ethylene glycol and/or 1, the 2-propylene glycol.
4. it is characterized in that in accordance with the method for claim 2: the concentration of sugar or sugar alcohol is 10-50%.
5. in accordance with the method for claim 1, it is characterized in that: described 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.
6. in accordance with the method for claim 5, it is characterized in that: in metal Ni, the mass content of catalyst activity component is 5-20%; Described promoter addition is the 0.2-8.0% of catalyst quality.
7. it is characterized in that in accordance with the method for claim 5: described molecular sieve is A type molecular sieve, X type molecular sieve, Y zeolite, β-molecular sieve, ZSM-5, MCM-41, SBA-15 molecular sieve.
8. in accordance with the method for claim 5; it is characterized in that: described 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.
9. it is characterized in that in accordance with the method for claim 1: 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.
10. it is characterized in that in accordance with the method for claim 1: catalyst consumption is the 3-10% of reaction system quality.
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| CN112090428A (en) * | 2019-06-18 | 2020-12-18 | 长春美禾科技发展有限公司 | Alloy catalyst and preparation method, related equipment and application thereof |
| CN112961038B (en) * | 2019-12-13 | 2022-04-19 | 中国科学院大连化学物理研究所 | Method for preparing mixed ether compound |
| CN112961038A (en) * | 2019-12-13 | 2021-06-15 | 中国科学院大连化学物理研究所 | Method for preparing mixed ether compound |
| CN112979429A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Tandem method and equipment for preparing glycol ether compound |
| CN112979429B (en) * | 2019-12-13 | 2022-06-03 | 中国科学院大连化学物理研究所 | Tandem method and equipment for preparing glycol ether compound |
| CN112044433A (en) * | 2020-09-21 | 2020-12-08 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing sorbitol and preparation method and application thereof |
| CN112044433B (en) * | 2020-09-21 | 2023-01-24 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing sorbitol and preparation method and application thereof |
| CN115005494A (en) * | 2022-06-30 | 2022-09-06 | 河南中烟工业有限责任公司 | Method for reducing cracking temperature of carbohydrate and application thereof |
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